Construction of all-organic low dielectric polyimide hybrids via synergistic effect between covalent organic framework and cross-linking structure

Polyimide(PI)is a promising electronic packaging material,but it remains challenging to obtain an all-organic PI hybrid film with decreased dielectric constant and loss without modifying the monomer.Herein,a series of allorganic PI hybrid films were successfully prepared by introducing the covalent organic framework(COF),which could induce the formation of the cross-linking structure in the PI matrix.Due to the synergistic effects of the COF fillers and the cross-linking structure,the PI/COF hybrid film containing 2 wt%COF exhibited the lowest dielectric constant of 2.72 and the lowest dielectric loss(tanδ)of 0.0077 at 1 MHz.It is attributed to the intrinsic low dielectric constant of COF and a large number of mesopores within the PI.Besides,the cross-linking network of PI prevents the molecular chains from stacking and improves the fraction of free volume(FFV).The molecular dynamics simulation results are well consistent with the dielectric properties data.Furthermore,the PI/COF hybrid film with 5 wt%COF showed a significant enhancement in breakdown strength,which increased to 412.8 kV/mm as compared with pure PI.In addition,the PI/COF hybrid film achieve to reduce the dielectric constant and thermal expansion coefficient(CTE).It also exhibited excellent thermal,hydrophobicity,and mechanical performance.The all-organic PI/COF hybrid films have great commercial potential as next-generation electronic packaging materials.

Recent advances in core-shell organic framework-based photocatalysts for energy conversion and environmental remediation

Direct conversion of solar energy into chemical energy in an environmentally friendly manner is one of the most promising strategies to deal with the environmental pollution and energy crisis.Among a variety of materials developed as photocatalysts,the core-shell metal/covalent-organic framework(MOF or COF)photocatalysts have garnered significant attention due to their highly porous structure and the adjustability in both structure and functionality.The existing reviews on core-shell organic framework photocatalytic materials have mainly focused on core-shell MOF materials.However,there is still a lack of indepth reviews specifically addressing the photocatalytic performance of core-shell COFs and MOFs@COFs.Simultaneously,there is an urgent need for a comprehensive review encompassing these three types of core-shell structures.Based on this,this review aims to provide a comprehensive understanding and useful guidelines for the exploration of suitable core-shell organic framework photocatalysts towards appropriate photocatalytic energy conversion and environmental governance.Firstly,the classification,synthesis,formation mechanisms,and reasonable regulation of core-shell organic framework were summarized.Then,the photocatalytic applications of these three kinds of core-shell structures in different areas,such as H_(2)evolution,CO_(2)reduction,and pollutants degradation are emphasized.Finally,the main challenges and development prospects of core-shell organic framework photocatalysts were introduced.This review aims to provide insights into the development of a novel generation of efficient and stable core-shell organic framework materials for energy conversion and environmental remediation.

Tuning the surface electronic structure of noble metal aerogels to promote the electrocatalytic oxygen reduction

The sluggish kinetics of the oxygen reduction reaction(ORR)is the bottleneck for various electrochemical energy conversion devices.Regulating the electronic structure of electrocatalysts by ligands has received particular attention in deriving valid ORR electrocatalysts.Here,the surface electronic structure of Ptbased noble metal aerogels(NMAs)was modulated by various organic ligands,among which the electron-withdrawing ligand of 4-methylphenylene effectively boosted the ORR electrocatalysis.Theoretical calculations suggested the smaller energy barrier for the transformation of O^(*) to OH^(*) and downshift the d-band center of Pt due to the interaction between 4-methylphenylene and the surface metals,thus enhancing the ORR intrinsic activity.Both Pt3Ni and Pt Pd aerogels with 4-methylphenylene decoration performed significant enhancement in ORR activity and durability in different media.Remarkably,the 4-methylphenylene modified Pt Pd aerogel exhibited the higher halfwave potential of 0.952 V and the mass activity of 10.2 times of commercial Pt/C.This work explained the effect of electronic structure on ORR electrocatalytic properties and would promote functionalized NMAs as efficient ORR electrocatalysts.

Boosting photocatalytic hydrogen evolution enabled by SiO_(2)-supporting chiral covalent organic frameworks with parallel stacking sequence

Two-dimensional covalent organic frameworks(2D COFs)feature extendedπ-conjugation and ordered stacking sequence,showing great promise for high-performance photocatalysis.Periodic atomic frameworks of 2D COFs facilitate the in-plane photogenerated charge transfer,but the precise ordered alignment is limited due to the non-covalentπ-stacking of COF layers,accordingly hindering out-of-plane transfer kinetics.Herein,we address a chiral induction method to construct a parallelly superimposed stacking chiral COF ultrathin shell on the support of SiO_(2) microsphere.Compared to the achiral COF analogues,the chiral COF shell with the parallel AA-stacking structure is more conducive to enhance the built-in electric field and accumulates photogenerated electrons for the rapid migration,thereby affording superior photocatalytic performance in hydrogen evolution from water splitting.Taking the simplest ketoenamine-linked chiral COF as a shell of SiO_(2) particle,the resulting composite exhibits an impressive hydrogen evolution rate of 107.1 mmol g^(-1)h^(-1)along with the apparent quantum efficiency of 14.31% at 475 nm.Furthermore,the composite photocatalysts could be fabricated into a film device,displaying a remarkable photocatalytic performance of 178.0 mmol m^(-2)h^(-1)for hydrogen evolution.Our work underpins the surface engineering of organic photocatalysts and illustrates the significance of COF stacking structures in regulating electronic properties.

Adsorption of volatile organic compounds on three activated carbon samples:Effect of pore structure

To investigate the influence of the activated carbon pore structure on the adsorption of volatile organic compounds （VOCs）, three commercial activated carbon samples were chosen. The fixed-bed thermostatic adsorption experiments were conducted under certain conditions, where toluene, acetone, and 1, 2-dichloroethane acted as adsorbents. Then, the incidence relation between the experimental results and the activated carbon pore structure was analyzed. After that, the results of the correlation analysis were verified in accordance with fractal theory and adsorption characteristic curve analysis. The results show that the pore diameter gradient is helpful for strengthening the intemal diffusion. Under the same condition, the adsorption of organic gases tends to be selective, and the positions of toluene, acetone and 1, 2-dichloroethane adsorbed on the activated carbon are mainly in the ranges of 1.27-1.49 nm, 0.67-0.84 nm and 1.39-1.75 nm, respectively. The relationship between adsorption capacity and activated carbon pore volume can accurately explain the spreading process of the adsorbents in the activated carbon.

Computer simulation of coal organic mass structure and its sorption properties

Structural model of C100H79O7NS coal organic mass was obtained within density functional theory in the localized orbital basis set using the B3LYP hybrid functional. The model was compared with the known experimental data for coal of different grades and its sorption properties were studied with respect to CH4, CO2 and H2O. It has been shown that macromolecule of coal organic mass has bulk structure with a pore inside it. Interaction between coal and CH4 molecules consists of typical physical adsorption with oligomer formation on the pore border, physical adsorption with elements of chemical adsorption was also observed between coal and H2O molecules. Interaction between coal and H2O molecules included both physical and chemical adsorbion.

Electronic structure engineering in organic thermoelectric materials

Electronic structures, which play a key role in determining electrical and optical properties of π-conjugated organic materials, have attracted tremendous interest. Efficient thermoelectric (TE) conversion of organic materials has rigorous requirements on electronic structures. Recently, the rational design and precise modulation of electronic structures have exhibited great potential in exploring state-of-the-art organic TE materials. This review focuses on the regulation of electronic structures of organic materials toward efficient TE conversion. First, we present the basic knowledge regarding electronic structures and the requirements for efficient TE conversion of organic materials, followed by a brief introduction of commonly used methods for electronic structure characterization. Next, we highlight the key strategies of electronic structure engineering for high-performance organic TE materials. Finally, an overview of the electronic structure engineering of organic TE materials, along with current challenges and future research directions, are provided.

Synthesis of spherical tremella-like Sb2O3 structures derived from metal-organic framworks and its lithium storage properties

A novel spherical tremella-like Sb2O3 was prepared by using metal-organic frameworks(MOFs)method under a mild liquid-phase reaction condition,and was further employed as an anode material for lithium-ion batteries(LIBs).The effect of reaction temperature and time on morphologies of Sb2O3 was studied.The results from SEM and TEM demonstrate that the tremella-like Sb2O3 architecture are composed of numerous nanosheets with high specific surface area.When the tremella-like Sb2O3 was used as LIBs anode,the discharge and charge capacities can achieve 724 and 446 mA·h/g in the first cycle,respectively.Moreover,the electrode retains an impressive high capacity of 275 mA·h/g even after 50 cycles at 20 mA/g,indicating that the material is extremely promising for application in LIBs.

Synthesis and Crystal Structure of a Magnesium Metal-organic Framework

A magnesium metal organic framework, [N-H2（CH3）2][-N（CH3）4][Mgs（bpdc）3（O2CH）6]· 3H2O （1, bpdcH2 = 4,4＇-biphenyldicarboxylic acid）, has been solvothermally synthesized and structurally characterized. 1 crystallizes in the trigonal system, space group R-3, with a = 11.3427（3）, c = 41.5662（18） A, V = 4631.3（3） A^3, Z = 3 and the final R = 0.0457. Its structure features a pillared-layered three-dimensional network with 8.21 A cavities, in which cationic [NH2（CH3）2]^＋ or [N（CH3）4]^＋ and lattice water molecules are located. Thermal stability of the title compound has also been investigated.

Microbial community structure and functional metabolic diversity are associated with organic carbon availability in an agricultural soil

Exploration of soil environmental characteristics governing soil microbial community structure and activity may improve our understanding of biogeochemical processes and soil quality. The impact of soil environmental characteristics especially organic carbon availability after 15-yr different organic and inorganic fertilizer inputs on soil bacterial community structure and functional metabolic diversity of soil microbial communities were evaluated in a 15-yr fertilizer experiment in Changping County, Beijing, China. The experiment was a wheat-maize rotation system which was established in 1991 including four different fertilizer treatments. These treatments included： a non-amended control（CK）, a commonly used application rate of inorganic fertilizer treatment（NPK）; a commonly used application rate of inorganic fertilizer with swine manure incorporated treatment（NPKM）, and a commonly used application rate of inorganic fertilizer with maize straw incorporated treatment（NPKS）. Denaturing gradient gel electrophoresis（DGGE） of the 16 S r RNA gene was used to determine the bacterial community structure and single carbon source utilization profiles were determined to characterize the microbial community functional metabolic diversity of different fertilizer treatments using Biolog Eco plates. The results indicated that long-term fertilized treatments significantly increased soil bacterial community structure compared to CK. The use of inorganic fertilizer with organic amendments incorporated for long term（NPKM, NPKS） significantly promoted soil bacterial structure than the application of inorganic fertilizer only（NPK）, and NPKM treatment was the most important driver for increases in the soil microbial community richness（S） and structural diversity（H）. Overall utilization of carbon sources by soil microbial communities（average well color development, AWCD） and microbial substrate utilization diversity and evenness indices（H＇ and E） indicated that long-term inorganic fertilizer with organic amendments incorporated（NPKM, NPKS） could significantly stimulate soil microbial metabolic activity and functional diversity relative to CK, while no differences of them were found between NPKS and NPK treatments. Principal component analysis（PCA） based on carbon source utilization profiles also showed significant separation of soil microbial community under long-term fertilization regimes and NPKM treatment was significantly separated from the other three treatments primarily according to the higher microbial utilization of carbohydrates, carboxylic acids, polymers, phenolic compounds, and amino acid, while higher utilization of amines/amides differed soil microbial community in NPKS treatment from those in the other three treatments. Redundancy analysis（RDA） indicated that soil organic carbon（SOC） availability, especially soil microbial biomass carbon（Cmic） and Cmic/SOC ratio are the key factors of soil environmental characteristics contributing to the increase of both soil microbial community structure and functional metabolic diversity in the long-term fertilization trial. Our results showed that long-term inorganic fertilizer and swine manure application could significantly improve soil bacterial community structure and soil microbial metabolic activity through the increases in SOC availability, which could provide insights into the sustainable management of China＇s soil resource.

Synthesis,Structure and Characterization of a 3D Chiral Carboxylate and Phosphonate Metalorganic Framework Based on 1,1?-Biphenol Ligand

A novel phosphonate-based chiral metal-organic framework 1 was synthesized from C2-symmetric 1,1？-biphenol-based ligand and structurally characterized by single-crystal and powder X-ray diffraction, Fourier-transform infrared spectra（FTIR）, circular dichroism（CD） and thermogravimetric analyses（TGA）. Two neighboring Mn ions are linked by two carboxylate groups and one phosphate group to form a di-manganese unit [Mn2] and each [Mn2] cluster in 1 is linked by five ligands, generating a 3D network with fns topology. In addition, the photoluminescence properties of 1 and H4 L were investigated.

Quasi-Three-Dimensional Cyclotriphosphazene-Based Covalent Organic Framework Nanosheet for Efficient Oxygen Reduction

Metal-free carbon-based materials are considered as promising oxygen reduction reaction(ORR)electrocatalysts for clean energy conversion,and their highly dense and exposed carbon active sites are crucial for efficient ORR.In this work,two unique quasi-three-dimensional cyclotriphosphazene-based covalent organic frameworks(Q3CTP-COFs)and their nanosheets were successfully synthesized and applied as ORR electrocatalysts.The abundant electrophilic structure in Q3CTP-COFs induces a high density of carbon active sites,and the unique bilayer stacking of[6+3]imine-linked backbone facilitates the exposure of active carbon sites and accelerates mass diffusion during ORR.In particular,bulk Q3CTP-COFs can be easily exfoliated into thin COF nanosheets(NSs)due to the weak interlayerπ-πinteractions.Q3CTP-COF NSs exhibit highly efficient ORR catalytic activity(half-wave potential of 0.72 V vs.RHE in alkaline electrolyte),which is one of the best COF-based ORR electrocatalysts reported so far.Furthermore,Q3CTP-COF NSs can serve as a promising cathode for Zn-air batteries(delivered power density of 156 mW cm-2 at 300 mA cm^(-2)).This judicious design and accurate synthesis of such COFs with highly dense and exposed active sites and their nanosheets will promote the development of metal-free carbon-based electrocatalysts.

Hydrothermal Synthesis,Structure and Properties of a 3D Pillar-layered Metal-organic Framework Based on Amino-arenedisulfonate Ligand

One novel metal-organic framework(MOF), [Ba(L)(HO)](1, HL =aniline-2,5-disulfonic acid), has been synthesized by hydrothermal method. Each barium atom is eleven-coordinated into a distorted monocapped pentagonal antiprismatic arrangement. Compound 1 shows an interesting 3 D pillar-layered structure constructed from 2 D inorganic layers[Ba(SO)(HO)]and organic pillars of phenyl moieties of L2-linkages. The inorganic layers are supported by the organic pillars, generating a novel 3 D open framework structure with {3, 4~6, 5~5, 6~5,7~4}2{3}{5} topology. The result of fluorescence measurement can reveal that the decayed emission band centered at 492 nm may be caused by the interactions of the ligands and the metal ions.Compound 1 exhibits selective toward the adsorption of COover Nat 273 K.

Synthesis and Crystal Structure of Organic Salt (H_2Bpy)(cda)_2 (cda = Carbamyldicyano-methanide Anion; H_2bpy = Hydrogen 4,4'-Bipyridyl Divalent Cation)

The organic salt, (H2Bpy)(cda)2, was synthesized by the reaction of sodium car- bamyldicyanomethanide, 4,4-bipyridyl and manganese(II) perchlorate in water solution. The crystal belongs to monoclinic, space group C2/c with a = 20.333(7), b = 6.177(2), c = 15.566(5) ? b = 116.860(5), V = 1744(1) ?, Z = 4, C18H14N8O2 (Mr = 374.37), Dc = 1.426 g/cm3, F(000) = 776, m = 0.100 mm-1 and l = 0.71073 ? The structure was refined to R = 0.0560 and wR = 0.1072 for 590 observed reflections (I > 2s(I)). Two nitrogen atoms of the 4,4?bipyridyl molecule bonded to two hydrogen ions, resulting this neutral molecule into a divalent cation. Through the interaction of colorless H2bpy cation and colorless cda anion the red neutral organic salt was formed.

Hydrothermal Synthesis and Characterization of a Novel Organically-templated Tungsten Heteropolyacid with a Microporous Structure

A microporous organically-templated tungsten heteropolyacid, (C2N2H10)2 [H2P2W18O62]?8H2O, with a new type was hydrothermally synthesized by using ethylenediamine as the structure-directing agent. Its structure was determined by single-crystal X-ray diffraction analysis. Crystal data: monoclinic, space group P21/c, a = 14.633(4), b = 19.432(5), c = 26.776(5) ?, β = 117.849(11)o, V = 6732(3) ?3, Z = 4, Mr = 4615.48, Dc = 4.554 g/cm3, μ(MoKα) = 30.781 mm-1, F(000) = 7976, the final R = 0.0678 and wR = 0.1359. The crystal of the title compound is constructed by Dawson anions and organic dications forming a novel “hollow” channel system.

Structure Prediction Based on Hydrophobic to Hydrophilic Volume Ratios in Small Molecule Amphiphilic Organic Crystals

The structure type for the crystal of 4,4'-bis-(2-hydroxy-ethoxyl)-biphenyl 1 has been predicted by using the previously developed interfacial model for small organic molecules. Based on the calculated hydrophobic to hydrophilic volume of 1, this model predicts the crystal structure to be of lamellar or bicontinuous type, which has been confirmed by the X-ray single-crystal structure analysis (C20H26O6, monoclinic, P21/C, a = 16.084(1), b = 6.0103(4), c = 9.6410(7) A, β9 = 103.014(2)°, V= 908.1(1) A3, Z = 2, Dc= 1.325 g/cm3, F(000)=388,μ = 0.097 mm-1, MoKα radiation, λ = 0.71073 A, R = 0.0382 and wR = 0.0882 with I > 2σ(I) for 7121 reflections collected, 1852 unique reflections and 170 parameters). As predicted, the hydrophobic and hydrophilic portions of 1 form in the lamellae. The same interfacial model is applied to other amphilphilic small molecule organic systems for structural type prediction.

A Novel Organic-Inorganic Complex: Synthesis and Crystal Structure of [Ca(DMSO)_5(H_2O)]_2SiMo_(12)O_(40)

A novel organic-inorganic complex [Ca(DMSO)5(H2O)]2SiMo12O40 was synthesized from CaCl2, DMSO and H4SiMo12O40nH2O in mixed solvent of acetonitrile and water. Its structure was characterized with elemental analysis, IR and X-ray diffraction analysis.

Studies on the Structure Evolvement of Organic Agricultural Industry in Taiwan and its Influential Factors

In order to study the development of organic agriculture in Taiwan in recent years,and based on relevant agriculture,economic and social statistics,the general scale of organic agriculture and industrial structure were treated with statistic analysis. Results suggest that the general scale of organic agriculture in Taiwan grew rapidly from 2004 to 2011. The certified organic farmers grew by 140. 59%,and the area with organic plantation grew by 302. 40%. The industrial structure has changed significantly as vegetables have become the No. 1 organic crop instead of rice. Besides of the four major crops,organic plantation has played an increasingly important role. Essential factors influencing the great-leap-forward development include the general trend of agricultural industrial structure adjustment,proliferation of management system and strategic opportunities brought by economic cycles.

Inner-pore reduction nucleation of palladium nanoparticles in highly conductive wurster-type covalent organic frameworks for efficient oxygen reduction electrocatalysis

Covalent organic frameworks(COFs)have emerged as a class of promising supports for electrocatalysis because of their advantages including good crystallinity,highly ordered pores,and structural diversity.However,their poor conductivity represents the main obstruction to their practical application.Here,we reported a novel synthesis strategy for synergistically endowing a triphenylamine-based COFs with improved electrical conductivity and excellent catalytic activity for oxygen reduction,via the in-situ redox deposition and confined growth of palladium nanoparticles inside the porous structure of COFs using reductive triphenylamine frameworks as reducing agent;meanwhile,the triphenylamine unit was oxidized to radical cation structure and affords radical cation COFs with conductivity as high as3.2*10^(-1) S m^(-1).Such a uniform confine palladium nanoparticle on highly conductive COFs makes it an efficient electrocatalyst for four-electron oxygen reduction reaction(4e-ORR),showing excellent activities and fast kinetics with a remarkable half-wave potential(E_(1/2))of 0.865 V and an ultralow Tafel slope of 39.7 mV dec^(-1) in alkaline media even in the absence of extra commercial conductive fillers.The generality of this strategy was proved by preparing the different metal and metal alloy nanoparticles supported on COFs(Au@COF,Pt@COF,AuPd@COF,AgPd@COF,and PtPd@COF)using reductive triphenylamine frameworks as reducing agent.This work not only provides a facile strategy for the fabrication of highly conductive COF supported ORR electrocatalysts,but also sheds new light on the practical application of Zn-air battery.

An ionic 2D inorganic-organic hybrid of tris[((1H-tetrazol-5-yl)methyl)morpholine] dodecatungstophosphate(Ⅴ) pentahydrate:Synthesis X-ray crystal structure and spectroscopic characterizations

A unique ionic hybrid material[C_6H_(12)N_5O]_3[(PO_4)W__(12)O_(36)]·5H_2O has been synthesized from the reaction of((1H-tetrazole-5- yl)methyl)morpholine andα-H_3[(PO_4)W_(12)O_(36)]·21H_2O.It has successfully been characterized by elemental analysis,IR and ~1H NMR spectroscopies,TGA and single-crystal X-ray diffraction method.The title compound is constructed from the three [C_6H_(12)N_5O]^+ cations andα-Keggin[(PO_4)W_(12)O_(36)]^(3-) polyoxoanion.The most remarkable structural feature of this hybrid can...