Preparation of Novel Organic Polymer Semiconductor and Its Properties in Transistors through Collaborative Theoretical and Experimental Approaches.

Conjugated polymer semiconductors based on donor-acceptor structures are commonly employed as core materials for optoelectronic devices in the field of organic electronics. In this study, we designed and synthesized a novel acceptor unit thiophene-vinyl-diketopyrrolopyrrole, named TVDPP, based on a four-step organic synthesis procedure. Stille coupling reactions were applied with high yields of polymerization of TVDPP with fluorinated thiophene (FT) monomer. The molecular weight and thermal stability of the polymers were tested and showed high molecular weight and good thermal stability. Theoretical simulation calculations and 2D grazing-incidence wide-angle X-ray scattering (GIWAXS) tests verified the planarity of the material and excellent stacking properties, which are favorable for achieving high carrier mobility. Measurements based on the polymer as an organic thin film transistor (OTFT) device were carried out, and the mobility and on/off current ratio reached 0.383 cm2 V-1 s-1 and 104, respectively, showing its great potential in organic optoelectronics.

Modification of Pillared Intercalated Montmorillonite Clay as Heterogeneous Pd Catalyst Supports.

Montmorillonite clay was modified by pillaring with AlMn oxides in different Al/Mn ratios and intercalation of two kinds of N-containing polymers (i.e., chitosan (CS) and polyvinyl pyrrolidinone (PVP)) chains. The modified pillared montmorillonite clay (PM) showed a rich two-dimensional layered porous structure with tunable parameters, such as large interlayer spacing, high specific area, and large porous volume. They were then used as supports for Pd nanoparticles. As applied in coupling reactions of aryl halides with terminal alkynes, Pd@CS/AlMn-PM showed better comprehensive catalytic performance than Pd@PVP/AlMn-PM. This was mainly attributed to its higher specific area, stronger chelation to Pd species, and better solvent resistance.

TiO2-Modified Montmorillonite-Supported Porous Carbon-Immobilized Pd Species Nanocomposite as an Efficient Catalyst for Sonogashira Reactions.

In this study, a combination of the porous carbon (PCN), montmorillonite (MMT), and TiO2 was synthesized into a composite immobilized Pd metal catalyst (TiO2-MMT/PCN@Pd) with effective synergism improvements in catalytic performance. The successful TiO2-pillaring modification for MMT, derivation of carbon from the biopolymer of chitosan, and immobilization of Pd species for the prepared TiO2-MMT/PCN@Pd0 nanocomposites were confirmed using a combined characterization with X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), N2 adsorption-desorption isotherms, high-resolution transition electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. It was shown that the combination of PCN, MMT, and TiO2 as a composite support for the stabilization of the Pd catalysts could synergistically improve the adsorption and catalytic properties. The resultant TiO2-MMT80/PCN20@Pd0 showed a high surface area of 108.9 m2/g. Furthermore, it exhibited moderate to excellent activity (59-99% yield) and high stability (recyclable 19 times) in the liquid-solid catalytic reactions, such as the Sonogashira reactions of aryl halides (I, Br) with terminal alkynes in organic solutions. The positron annihilation lifetime spectroscopy (PALS) characterization sensitively detected the development of sub-nanoscale microdefects in the catalyst after long-term recycling service. This study provided direct evidence for the formation of some larger-sized microdefects during sequential recycling, which would act as leaching channels for loaded molecules, including active Pd species.

Preparation of Dye Semiconductors via Coupling Polymerization Catalyzed by Two Catalysts and Application to Transistor.

Organic dye semiconductors have received increasing attention as the next generation of semiconductors, and one of their potential applications is as a core component of organic transistors. In this study, two novel diketopyrrolopyrrole (DPP) dye core-based materials were designed and separately prepared using Stille coupling reactions under different palladium catalyst conditions. The molecular weights and elemental compositions were tested to demonstrate that both catalysts could be used to successfully prepare materials of this structure, with the main differences being the weight-average molecular weight and the dispersion index. PDPP-2Py-2Tz I with a longer conjugation length exhibited better thermodynamic stability than the counterpart polymer PDPP-2Py-2Tz II. The intrinsic optical properties of the polymers were relatively similar, while the electrochemical tests showed small differences in their energy levels. The polymers obtained with different catalysts displayed similar and moderate electron mobility in transistor devices, while PDPP-2Py-2Tz I possessed a higher switching ratio. Our study provides a comparison of such dye materials under different catalytic conditions and also demonstrates the great potential of dye materials for optoelectronic applications.

Novel Divinyl-Flanked Diketopyrrolopyrrole Polymer, Based on a Dimerization Strategy for High-Performance Organic Field-Effect Transistors.

In this communication, we report a novel acceptor structural unit, TVDPP, that can be distinguished from classical materials based on TDPP structures. By designing a synthetic route via retrosynthetic analysis, we successfully prepared this monomer and further prepared polymer P2TVDPP with high yield using a Stille-coupling polymerization reaction. The polymer showed several expected properties, such as high molecular weight, thermal stability, full planarity, small π-π stacking distance, smooth interface, and so on. The absorption spectra and energy levels of the polymer were characterized via photochemical and electrochemical analysis. The organic field-effect transistor (OFET), which is based on P2TVDPP, exhibited excellent carrier mobility and an on/off current ratio of 0.41 cm2 V-1 s-1 and ~107, respectively, which is an important step in expanding the significance of DPP-based materials in the field of optoelectronic devices and organic electronics.

Novel bio-inspired three-dimensional nanocomposites based on montmorillonite and chitosan.

In this study, inspired by nacre-like structural natural shells, novel three-dimensional (3D) nanocomposites based on natural nanoplatelets of montmorillonite (MMT) and polysaccharide of chitosan (CS) were prepared with solution intercalation and self-assembly process. The CS-intercalated-MMT nanoplatelets units acted as "bricks" and CS molecules acted as "mortar", arranging in fairly well-ordered layered structure. With addition of glutaraldehyde (GA) and Pd2+ cations, synergistic toughening and strengthening effects of covalent and ionic bonds could be achieved. The best mechanical properties of the prepared 3D nanocomposites were observed as 5.6 KJ/m2 (impact strength), 3.3 GPa (flexural modulus), and 65.8 MPa (flexural strength), respectively, which showed higher toughness but lower flexural properties than natural pearl mussel shells. Nevertheless, both the impact and flexural properties of the prepared 3D nanocomposite were much higher than the other natural shell, i.e. green grab shell. Besides conventional methods characterizations, the nacre-like structure of the artificial 3D nanocomposite was further evidenced with positron annihilation lifetime spectroscopy characterizations. This work might facilitate a versatile platform for developing green 3D bionanocomposites with fairly good mechanical properties.

Chitosan modified Ti-PILC supported PdOx catalysts for coupling reactions of aryl halides with terminal alkynes.

Biopolymer of chitosan (CS) and titanium pillared clays (Ti-PILCs) have been combined in a hybrid as advanced supports for immobilization of PdOx=0,1 species to prepare novel PdOx=0,1@Ti-PILC/CS nano-composite catalysts. The Ti-PILC materials showed high specific surface areas and abundant meso-porous structure with many irregular pore channels caused by collapses of layered structure of clay during Ti pillaring process. Both CS chains and sub-nano sized PdOx particles were successfully incorporated into the pore channels of Ti-PILC, resulting in a decrease in both the specific surface areas and uniform distribution of pore size. Besides conventional methods characterizations, the strong interactions between PdOx species and Ti-PILC/CS support were further evidenced with positron annihilation lifetime spectroscopy studies. The resultant PdOx@Ti-PILC/CS catalyst was highly active for the coupling reactions of aryl halides with phenyl acetylenes. It was recyclable and gave excellent yield up to 13 runs with low leaching of Pd species.

Preparation of porous chitosan/reduced graphene oxide microspheres supported Pd nanoparticles catalysts for Heck coupling reactions.

Novel porous chitosan/reduced graphene oxide microspheres supported Pd nanoparticles catalysts (Pd@CS/RGO) were prepared by a combination of silica nanoparticles etching and freeze-drying treatments of CS/RGO/silica/PdCl2 composite microspheres. The microstructure of the Pd@CS/RGO microspheres catalysts have been investigated by X-ray photo electron spectroscopy (XPS), Raman spectroscopy, high resolution transmission electron microscopy (HR-TEM), thermo-gravimetric analysis (TGA), and X-ray diffraction (XRD), etc. The results revealed that: the novel catalysts showed open porous structure; CS had good miscibility with RGO nanosheets; Pd nanoparticles were well incorporated within CS/RGO matrix; the thermal stabilities of the catalysts were improved significantly over CS. Meanwhile, the Pd@CS/RGO catalysts have been demonstrated as highly active and easily recyclable catalysts for Heck reactions. The preparation process is simple, and the structure and performance of the catalytic material can be governed by changing the mass ratios of CS/RGO/silica/PdCl2 and the pore-forming process conditions.

Modification of Montmorillonite with Polyethylene Oxide and Its Use as Support for Pd0 Nanoparticle Catalysts.

In this study, montmorillonite (MMT) was modified by intercalating polyethylene oxide (PEO) macromolecules between the interlayer spaces in an MMT-water suspension system. X-ray diffraction results revealed that the galleries of MMT were expanded significantly after intercalation of different loading of PEO. MMT/PEO 80/20 composite was chosen as the support platform for immobilization of Pd species in preparing novel heterogeneous catalysts. After immobilization of Pd species, the interlayer spacing of MMT/PEO (80/20) (1.52 nm) was further increased to 1.72 nm (Pd2+@MMT/PEO) and 1.73 nm (Pd0@MMT/PEO), confirming the well-immobilization of the Pd species in the interlayer spaces of PEO-modified MMT. High-resolution transmission electron microscopy (HR-TEM) observation results confirmed that Pd nanoparticles were confined inside the interlayer space of MMT and/or dispersed well on the outer surface of MMT. The conversion of Pd2+ to Pd0 species was evidenced by binding energy characterization with X-ray photo electron spectroscopy (XPS). The microstructure variation caused by the Pd immobilization was sensitively detected by positron annihilation lifetime spectroscopy (PALS) studies. The prepared Pd0@MMT/PEO (0.2/80/20) catalytic composite exhibits good thermal stability up to around 200 °C, and it showed high activities for Heck reactions between aryl iodides and butyl acrylates and could be recycled for five times. The correlations between the microstructure and properties of the Pd@MMT/PEO catalytic composites were discussed.

One-pot carbonization of chitosan/P123/PdCl2 blend hydrogel membranes to N-doped carbon supported Pd catalytic composites for Ullmann reactions.

Novel porous nitrogen-doped carbon supported Pd (Pd@N-C) catalytic composites were prepared by one-pot thermal carbonization of chitosan/poly(ethylene glycol)­block­poly(propylene glycol)­block­poly(ethylene glycol)/PdCl2 (CS/P123/PdCl2) blend hydrogel membranes at different temperature in N2 atmosphere. The porous structure of the Pd@N-C catalytic composite was governed by both the addition of P123 and the carbonization temperature. At highest carbonization temperature of 900 °C, the prepared Pd@N-C catalytic composite from CS/P123/PdCl2 blend membrane showed the highest specific area (SBET) of 293.7 m2/g and total volume of pores (Vtot) of 0.79 cm3/g. The chemical state of the elements of C, N, O, Pd within the Pd@N-C catalytic composites were confirmed with X-ray photoelectron spectroscopy (XPS) measurements. Raman spectrum results showed that the prepared Pd@N-C catalytic composite contained mainly disordered carbon together with some graphite carbon. Pd nanoparticles sized in 5-20 nm dispersed well on the porous matrix of the carbon. The Pd@N-C catalytic composites showed excellent activities for the Ullmann homo-coupling reactions of aromatic halides, and can be recycled for 10 times. In such one-pot carbonization process, the polymer porogen is simultaneously decomposed without further etching and removal steps, which simplifies the preparation process and is beneficial to obtain Pd@N-C catalytic composites with desirable Pd loading.

Microstructure and catalytic performances of chitosan intercalated montmorillonite supported palladium (0) and copper (II) catalysts for Sonogashira reactions.

In this study, an efficient heterogeneous catalytic material including Pd0 nanoparticles and Cu2+ cations supported on montmorillonite/chitosan (MMT/CS) composite was prepared by solution intercalation and complexion methods. The valence states of Pd (both Pd(0) and Pd(II) coexisting) and Cu (mainly Cu(II)) of the Pd0/Cu2+@MMT/CS catalyst were confirmed by the X-ray photoelectron spectroscopy (XPS) characterization. The d001 spacing was enlarged from 1.25nm (MMT) to 1.94nm (Pd0/Cu2+@MMT/CS). Pd0/Cu2+@MMT/CS catalyst had obviously bigger specific surface area (SBET) and total pore volume (Vp) than pure MMT. High resolution transmission electron microscopy (HR-TEM) observation of the Pd0/Cu2+@MMT/CS catalyst showed that separated Pd0 nanoparticles sized below 3nm dispersed well both in the interlayer space and surface of MMT layers. The positron annihilation lifetime spectroscopy (PALS) was very sensitive to the microstructure changes caused by the formation of nano particles Pd0 after reduction of Pd2+/Cu2+@MMT/CS to Pd0/Cu2+@MMT/CS. The prepared Pd0/Cu2+@MMT/CS catalysts are highly active for the Sonogashira reactions of aromatic halides and alkynes in H2O/ether solution, and can be recycled 6 times. The leaching of Cu species is much quicker than Pd species during recycling, which should be the main reason for the decrease in efficiency of the recycled Pd0/Cu2+@MMT/CS catalysts.

Heterogeneous Catalytic Composites from Palladium Nanoparticles in Montmorillonite Intercalated with Poly (Vinyl Pyrrolidone) Chains.

In this study, poly (vinyl pyrrolidone) (PVP) chains intercalated montmorillonite (MMT) matrices has been demonstrated as an excellent scaffolding material for the immobilization of palladium (Pd) nanoparticles to prepare efficient heterogeneous catalysts for Heck reactions. Multiple layers (up to four) of PVP chains can intercalate the interlayer space of the MMT, resulting in an increase therein from 1.25 to 3.22 nm. MMT/PVP with PVP loading (20%) was selected as the platform for the immobilization of Pd. The in-situ reduction of the chelated Pd2+ into Pd° in the interlayer space of MMT/PVP composite could be easily achieved. For the prepared Pd@MMT/PVP catalytic composite, a unique maze-like microstructure of Pd nanoparticles tightly encaged by PVP chains and by lamellae of layered silica has been detected by high resolution transmission electron microscopy (HR-TEM) and X-ray diffraction (XRD). Furthermore, the microstructure is well elucidated in molecular level by positron annihilation lifetime analysis of the Pd@MMT/PVP catalytic composite. The prepared Pd@MMT/PVP catalysts were highly active for the Heck coupling reactions between aromatic halides and alkenes, and could be recycled 9 times without significant decreases in coupling yields. The excellent comprehensive catalytic performances of the Pd@MMT/PVP catalytic composites are mainly attributed to their unique maze-like microstructure.

Insightful understanding of the correlations of the microstructure and catalytic performances of Pd@chitosan membrane catalysts studied by positron annihilation spectroscopy.

In this study, the catalytic performances of palladium supported on chitosan (Pd@CS) membrane heterogeneous catalysts have been studied from the aspects of free volume by positron annihilation lifetime spectroscopy (PALS). The results showed that the variation in free volume hole size of the Pd@CS membrane catalyst was closely associated with microstructure evolutions, such as increase of Pd content, valence transition of Pd by reduction treatment, solvent swelling, physical aging during catalyst recycling, and so on. The PALS results showed that both the mean free volume hole size of the Pd0@CS membrane in the dry or swollen state (analyzed by the LT program) and its distribution (analyzed by the MELT program) are smaller than the molecule size of the reactants and products in the catalysis reaction. However, the results showed that the Pd0@CS membrane catalyst has excellent catalytic activity for the Heck coupling reaction of all the reactants with different molecule size. It was revealed that the molecule transport channels of the Pd0@CS membrane catalyst in the reaction at high temperature was through a number of instantaneously connected free volume holes rather than a single free volume hole. This hypothesis was powerfully supported by the catalytic activity assessment results of the CS layer sealed Pd0@CS membrane catalyst. Meanwhile, it was confirmed that the leaching of Pd0 nanoparticles of the reused Pd0@CS membrane catalyst during the recycling process was also through such instantaneously connected free volume holes.

Co-immobilization of Pd and Zn nanoparticles in chitosan/silica membranes for efficient, recyclable catalysts used in ullmann reaction.

In this study, an efficient heterogeneous catalyst including palladium (Pd) and zinc (Zn) nanoparticles supported on chitosan/silica (CS/SiO2) composite membrane is synthesized using partially etching of SiO2 technique. N2 sorption isotherm results shows that the prepared Pd-Zn@CS/SiO2 (1/1) porous membrane had a BET surface area of 26.50m2/g. High-resolution transmission electron microscopy (HR-TEM) and X-ray photoelectron spectroscopy (XPS), characterization of the catalyst shows that the Pd0 nanoparticles (below 5nm), and Zn0 aggregates (about 10-15nm) dispersed well in the CS/SiO2 matrix. Zinc crystal was also detected by X-ray diffraction study and HR-TEM observation. The prepared Pd-Zn@CS/SiO2 membrane catalyst is highly active for Ullmann reductive homocoupling reactions of aryl iodides and aryl bromides, and can be recycled 5 times without significant loss of activities. This work supplies a successful approach to realize Pd catalysts and Zn reducing reagent co-immobilized in the same carrier material with excellent catalytic performances.

Probing sub-nano level molecular packing and correlated positron annihilation characteristics of ionic cross-linked chitosan membranes using positron annihilation spectroscopy.

Chitosan, CS, cross-linked with bivalent palladium has shown enhanced mechanical and thermal properties depending on the transformation of the structure at a microscopic scale. In the present study, CS directly cross-linked by palladium cation membranes (CS-cr-PM) was prepared through a solution-casting method. Mobility of chitosan chains were greatly reduced after crosslinking, making a great reduction in the swelling ratio studied by a water-swelling degree measurement, which led to an improvement in molecular chain rigidity. In order to investigate the chain packing at the molecular level in the ionic cross-linked CS system, the structure of chemically-crosslinked CS is investigated by means of the combined use of wide angle X-ray diffraction (WAXD) and infrared measurements, and a combination of positron annihilation lifetime spectroscopy (PALS) and simultaneous coincidence Doppler broadening (CDB) spectroscopy offers coherent information on both the free-volume related sub-nano level molecular packing and the chemical surrounding of free volume nanoholes in CS-cr-PM as a function of palladium salt loading. The variations in the free volume size and size distribution have been determined through the ortho-positronium (o-Ps) lifetime and its lifetime distribution. The studies showed that a strong interaction between CS molecules and palladium cations results in the change in crystallinity in formed CS-cr-PM leading to variational chain packing density. Meanwhile, significant inhibition effects on positronium formation due to doping are observed, which could be interpreted in terms of the existence of chloride ions. Applications of positron annihilation spectroscopy to study the microstructure and correlated positron annihilation characteristics of an ionic cross-linked CS system are systematically discussed.

Encaging Palladium Nanoparticles in Chitosan Modified Montmorillonite for Efficient, Recyclable Catalysts.

Metal nanoparticles, once supported by a suitable scaffolding material, can be used as highly efficient heterogeneous catalysts for numerous organic reactions. The challenge, though, is to mitigate the continuous loss of metals from the supporting materials as reactions proceed, so that the catalysts can be recycled multiple times. Herein, we combine the excellent chelating property of chitosan (CS) and remarkable stability of montmorillonite (MMT) into a composite material to support metal catalysts such as palladium (Pd). The in situ reduction of Pd2+ into Pd0 in the interstices of MMT/CS composites effectively encages the Pd0 nanoparticles in the porous matrices, while still allowing for reactant and product molecules of relatively small sizes to diffuse in and out the matrices. The prepared Pd0@MMT/CS catalysts are highly active for the Heck reactions of aromatic halides and alkenes, and can be recycled 30 times without significant loss of activities. Positron annihilation lifetime analysis and other structural characterization methods are implemented to elucidate the unique compartmentalization of metal catalysts in the composite matrices. As both CS and MMT are economical and abundant materials in nature, this approach may facilitate a versatile platform for developing highly recyclable, heterogeneous catalysts containing metal nanoparticles.

N-doped mesoporous carbons supported palladium catalysts prepared from chitosan/silica/palladium gel beads.

In this study, a heterogeneous catalyst including palladium nanoparticles supported on nitrogen-doped mesoporous carbon (Pd@N-C) is synthesized from palladium salts as palladium precursor, colloidal silica as template, and chitosan as carbon source. N2 sorption isotherm results show that the prepared Pd@N-C had a high BET surface area (640m(2)g(-1)) with large porosity. The prepared Pd@N-C is high nitrogen-rich as characterized with element analysis. X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HR-TEM), and Raman spectroscopy characterization of the catalyst shows that the palladium species with different chemical states are well dispersed on the nitrogen-containing mesoporous carbon. The Pd@N-C is high active and shows excellent stability as applied in Heck coupling reactions. This work supplies a successful method to prepare Pd heterogeneous catalysts with high performance from bulk biopolymer/Pd to high porous nitrogen-doped carbon supported palladium catalytic materials.

Novel macroporous palladium cation crosslinked chitosan membranes for heterogeneous catalysis application.

A novel palladium supported on chitosan porous membrane heterogeneous catalyst has been prepared by freeze-drying of Pd(2+)-crosslinked chitosan gel solution. The prepared membrane catalyst has three-dimensional porous structure (porosity: >70%). The crosslinking effects of Pd(2+) to chitosan were good for the improvement of the mechanical properties and thermal stabilities. Pd(2+) cations have been shown not only as the crosslinker, but also as the catalytic active sites. The reductive palladium species of the recycled membrane catalysts was found in the nanometer scale (20-40nm). Excellent cross-coupling yields were achieved using as low as 0.12mol% palladium catalyst loading for the Heck-type reaction of aromatic halides with acrylates. The catalyst could be recycled six times without obvious decreased conversion.

Chitosan microspheres supported palladium heterogeneous catalysts modified with pearl shell powders.

Significant enhancement of the catalytic stability and activity was obtained for the heterogeneous palladium catalyst supported on the shell powders-reinforced chitosan microspheres. For example, over 90% cross-coupling yields were achieved using as low as 0.05 mol% palladium catalyst loading for the Heck-type reaction of iodobenzene with n-butyl acrylate. Such significant enhancement of the catalytic stability and activity can be attributed to the intermolecular interactions of the surface polar molecules of the incorporated shell powders with the surrounding chitosan molecules as well as the deposited palladium species.

Microstructure-stability relations studies of porous chitosan microspheres supported palladium catalysts.

In this study, polyethylene glycol (PEG) with different molecular weight, polyvinyl pyrrolidone (PVP), and polyvinyl alcohol (PVA), are chosen as porogens for preparing chitosan base porous microsphere supported palladium catalyst for coupling reactions. The pore structure of the microspheres was controlled by the compatibility of chitosan and counterpart polymers. The prepared porous chitosan microspheres supported palladium heterogeneous catalysts have been evaluated using the well-established Ullmann reductive homocoupling and the Heck cross-coupling reactions. The activities, stabilities and recyclability of the porous chitosan microspheres supported palladium catalysts are not only highly dependent upon the surface areas of the solid supports, but also upon the chemical properties of the water-soluble polymers. The degradation of the prepared heterogeneous palladium catalysts is mainly caused by a combination of the palladium leaching and the morphological transformation of the palladium species from the amorphous into the crystals.