Liquid-phase synthesis of Li_(2)S and Li_(3)PS_(4) with lithium-based organic solutions

Sulfide solid electrolytes are widely regarded as one of the most promising technical routes to realize all-solid-state batteries(ASSBs)due to their high ionic conductivity and favorable deformability.However,the relatively high price of the crucial starting material,Li_(2)S,results in high costs of sulfide solid electrolytes,limiting their practical application in ASSBs.To solve this problem,we develop a new synthesis route of Li_(2)S via liquid-phase synthesis method,employing lithium and biphenyl in 1,2-dimethoxyethane(DME)ether solvent to form a lithium solution as the lithium precursor.Because of the comparatively strong reducibility of the lithium solution,its reaction with sulfur proceeds effectively even at room temperature.This new synthesis route of Li_(2)S starts with cheap precursors of lithium,sulfur,biphenyl and DME solvent,and the only remaining byproduct(DME solution of biphenyl)after the collection of Li_(2)S product can be recycled and reused.Besides,the reaction can proceed effectively at room temperature with mild condition,reducing energy cost to a great extent.The as-synthesized Li_(2)S owns uniform and extremely small particle size,proved to be feasible in synthesizing sulfide solid electrolytes(such as the solid-state synthesis of Li_(6)PS_(5)C_(l)).Spontaneously,this lithium solution can be directly employed in the synthesis of Li_(3)PS_(4) solid electrolytes via liquid-phase synthesis method,in which the centrifugation and heat treatment processes of Li_(2)S are not necessary,providing simplified production process.The as-synthesized Li_(3)PS_(4) exhibits typical Li+conductivity of 1.85×10^(-4) S·cm^(-1) at 30℃.

Synthesis strategies of covalent organic frameworks: An overview from nonconventional heating methods and reaction media

Covalent organic frameworks(COFs), as an emerging class of porous crystalline materials constructed by covalent links between the building monomers, have gained tremendous attention. Over the past 15 years, COFs have made rapid progress and substantial development in the chemistry and materials fields. However, the synthesis of COFs has been dominated by solvothermal methods for a long time and it usually involves high temperature, high pressure and toxic organic solvents, which created many challenges for environmental considerations. Recently,the exploration of new approaches for facile fabrication of COFs has aroused extensive interest. Hence, in this review, we comprehensively describe the synthetic strategies of COFs from the aspects of nonconventional heating methods and reaction media. In addition, the advantages,limitations and properties of the preparation methods are compared. Finally, we outline the main challenges and development prospects of the synthesis of COFs in the future and propose some possible solutions.

Water-based synthesis of nanoscale hierarchical metal-organic frameworks:Boosting adsorption and catalytic performance

The combination of nano sizes,large pore sizes and green synthesis is recognized as one of the most crucial and challenging problems in constructing metal-organic frameworks(MOFs).Herein,a water-based strategy is proposed for the synthesis of nanoscale hierarchical MOFs(NH-MOFs)with high crystallinity and excellent stability.This approach allows the morphology and porosity of MOFs to be fine tuned,thereby enabling the nanoscale crystal generation and a well-defined hierarchical system.The aqueous solution facilitates rapid nucleation kinetics,and the introduced modulator acts as a deprotonation agent to accelerate the deprotonation of the organic ligand as well as a structure-directing agent(SDA)to guide the formation of hierarchical networks.The assynthesized NH-MOFs(NH-ZIF-67)were assessed as efficient adsorbents and heterogeneous catalysts to facilitate the diffusion of guest molecules,outperforming the parent microZIF-67.This study focuses on understanding the NH-MOF growth rules,which could allow tailor-designing NH-MOFs for various functions.

Recent advances in the synthesis of nanoscale hierarchically porous metal–organic frameworks

Nanoscale hierarchically porous metal–organic frameworks(NHP-MOFs)have received unprecedented attention in many fields owing to their integration of the strengths of nanoscale size(<1μm)and hierarchical porous structure(micro-,meso-and/or macro-pores)of MOFs.This review focuses on recent advances in the main synthetic strategies for NHP-MOFs based on different metal ions(e.g.,Cu,Fe,Co,Zn,Al,Zr,and Cr),including the template method,composite technology,post-synthetic modification,in situ growth and the grind method.In addition,the mechanisms of synthesis,regulation techniques and the advantages and disadvantages of various methods are discussed.Finally,the challenges and prospects of the commercialisation of promising NHP-MOFs are also presented.The purpose of this review is to provide a road map for future design and development of NHP-MOFs for practical application.

Effect of different organic compounds on the preparation of CaO-based CO_(2) sorbents derived from wet mixing combustion synthesis

CaO based sorbents have great potential for commercial use to capture CO_(2) of power plants.In the demand of producing sorbents with better cyclic performance,CaO-based sorbents derived from different kinds of calcium precursors,containing calcium carbonate(CC-CaO),calcium gluconate monohydrate(CG-CaO),calcium citrate(CCi-CaO)and calcium acetate monohydrate(CA-CaO),were tested cyclically and compared using simultaneous thermal analyzer(STA).And further study was conducted on the sorbents modified with citric acid monohydrate and 50%gluconic acid solution by wet mixing combustion synthesis.The modified sorbents showed better performance and higher pore parameters as well as porous microstructure with more organic acid added.After 20 cycles of carbonation and calcination,the C2CCi8(CaO:citric acid=2:8 by mass ratio)and C2G8(CaO:gluconic acid=2:8 by mass ratio)sorbent possess CO_(2) capture capacity of 0.45g·g^(-1)(g CO_(2) per g sorbents)and 0.52 g·g^(-1) respectively.The citric acid was more effective for modification than gluconic acid for extended 50 cycles.Furthermore,good linear relationship between CaO conversion and specific surface area as well as pore volume were determined,of which the specific surface area showed closer correlation with CaO conversion。

Synthesis and Spectral Properties of Mixed-Ligand Complexes of Lanthanide Perchlorate with Bis-(phenylsulfinyl)ethane and Organic Lewis Bases

Six lanthanide complexes with bis(phenylsulfinyl)ethane(bphse) and organic bases(phen: 1,10 phenanthroline and bipy: 2,2'-bipyridine) were synthesized and characterized by elemental analysis, conductance and spectral (IR, UV Visible) data. The complexes were Ln(bphse) 2(bipy)(ClO 4) 3· n H 2O and Ln 2(bphse) 3(phen) 2(ClO 4) 6·H 2O(where Ln=Nd, Eu and Gd; n =0～2). IR spectral data confirmed that the lanthanide ions were coordinated by oxygen atoms from bphse and nitrogen atoms from phen or bipy. Exitation and emission spectra of Eu complexes were measured and discussed.

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.

Synthesis and Structural Chemistry of Two Novel Transition Metal Organic Phosphonates

Two novel transition metal phosphonate compounds, [Co（H2BDPP）（phen）]n 1 （BDPP = p-O3PCH2（C6H4）CH2PO3, phen = 1,10-phenanthroline） and [Pb3（BCP）2]n 2 （BCP = OOC（C6H4）CH2PO3）, have been synthesized and structurally determined by X-ray single-crystal diffraction. Compound 1 crystallizes in the monoclinic system, space group C2/c with a = 21.169（4）, b = 12.001（2）, c = 7.6211（15）A, β = 98.03（3）°, V= 1917.2（6）A^3, C20H18N2O6P2Co, Mr = 505.22, Z = 8, De= 1.737 g/cm^3, p = 1.107 mm^-1, F（000） = 1020, the final R= 0.0450 and wR = 0.1306 for 2072 observed reflections （I 〉 2σ（I）. Compound 2 crystallizes in the monoclinic system, space group C2/c with a = 4.7167（9）, b = 18.753（2）, c = 22.781（3）A, β = 91.07（3）°, V= 2014.7（14）A^, C8H6O5PPb1.5, Mr = 523.88, Z = 8, Dc = 3.454 g/cm^3, p = 25.222 mm^-1, F（000） = 1856, the final R = 0.0441 and wR = 0.1906 for 2259 observed reflections （I 〉 2σ（I）. In compound 1, the 1D chain running along the c axis is bridged by four ligands （trans- HO3PCH2C6H4CH2PO3H） in four different directions to extend the structure into a three- dimensional network. In compound 2, the Pb（II） displays 4- and 5-coordination modes. There is a one-dimensional P-O-Pb band along the a axis formed by PO3 groups and Pb（II） cations. These bands are joined by μ2-O of -COO to yield two-dimensional inorganic P-O-Pb layers which are pillared by the OOCC6HaCH2PO3 ligands to form a three-dimensional network. Moreover, compound 2 displays a strong emission band attributed to the ligand-centered （LC） transition.

Synthesis of Single Hexagonal-Phase AlN Nanocrystallines by a Liquid-Solid Metathetical Reaction in an Organic Solution

A liquid-solid metathetical reaction method （LSMRM） of synthesizing AIN nanocrystallines is presented. AIN nanocrystallines made through LSMRM are characterized by X-ray diffractions （XRD）, X-ray photoelectron spectroscopy （XPS）, transmission electron microscopy （TEM）, Fourier transformation infrared （FT-IR） spectroscopy, and Raman spectroscopy. The results show that the samples are single hexagonal-phase AIN and the size of the AIN samples is about tens of nanometer.

Poly(ethylene glycol)-supported Liquid-phase Parallel Synthesis of Di(aryloxyacetyl)thiosemicarbazides

An efficient poly(ethylene glycol) (PEG)-supported liquid-phase parallel approach to di(aryloxyacetyl)thiosemicarbazides is described. PEG-bound phenol reacted with chloroacetic acid to afford PEG-bound phenyloxyacetic acid, which was readily converted into corresponding phenyloxyacetyl chloride. Subsequent nucleophilic substitution with ammonium thiocyanate followed by addition of aryloxyacetic acid hydrazides gave PEG-bound di(aryloxyacetyl)thiosemi-carbazides, which were easily cleaved to give the resulting library of 1-aryloxyacetyl-4-(4'-methoxylcarbonylphenyloxyacetyl)thiosemicarbazides in good to high yield and high purity.

Synthesis and Performance Evaluation of Organic Bentonite Modifier Dimethyldistearylammonium Bromide (DODMAB)

Dimethyldistearylammonium Bromide (DODMAB) is a bentonite modifier with good performance. In this experiment, 1-Bromooctadecane is the raw material, and completes tertiary amination and quaternization successively by changing the condition of experiment. The result is that the productivity can achieve 78.94% in the synthesis of DODMAB. It has been used in the experiment of bentonite modification and achieves good results;compared with using trimethylstearylammonium bromide as the organic modifier, the synthetic organic bentonite has better performance than the common organic modifier when used in the oil base drilling fluid of oilfield operation.

REDUCTION BY HYPOPHOSPHOROUS ACID IN ORGANIC SYNTHESIS

Hypophosphorous acid and its salt were found to serve as a new agent for selective reduction of α,β-unsaturated carbonyl compounds under mild reaction conditions.

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.

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.

Chemoenzymatic Synthesis of Cellular Adhesion Tripeptide RGD Precursor in Organic Media

Chemoenzymatic synthesis of tripeptide Bz-RGD-（OEt）2 was conducted in this study. First, the free dipeptide Gly-Asp was synthesized via a novel chemical method, wherein only L-aspaxtic acid was used and was followed by the esterification of Gly-Asp. The formation of the linkage between the third amino acid Bz-Arg-OEt and Gly-Asp-（OEt）2 was completed by using the enzymatic method in organic media. The effects of several factors such as pH, the water content, triethylamine （TEA）, the molar ratio of the substrates, and the reaction time on the yield of Bz-RGD- （OEt）2 were examined. It was obtained that the optimum conditions for Bz-RGD-（OEt）2 synthesis in an ethanol/ Tris-HC1 buffer system （ volume ratio 93： 7 ） were as follows ： pH = 8.0 ; temperature, 30 ℃ ; reaction time, 7 h. The tripeptide yield was 75.2%.

Synthesis and Characteristics of Organic Bentonite Gel

The bentonite was modified using Ca-bentonite as a matrix and octadecyl/ hexndecyl ammonium chloride as the cover agent, based on hydrothermal process. The organic gel with 5.0 Pa· s viscosity was synthesized by dispersing it into the dimethyl benzene- methyl alcohol system fully. The optimum process conditions for organic modification were that the coating agent dosage is 22g/ L, reaction time is 90 minutes and the pH value of pulp is 10. X-ray diffraction （ XRD ） analysis indicates that the d （001） value of the modified bentonite is 20. 532 A. The influence of gel temperature on its viscosity characteristic was studied. By analyzing the transmssion electron microscopy （TEM） images and observing the dispersed gel, the nanometer effect of the organic gel was discussed.

Synthesis of Pyrazolines Used as Blue Organic Electroluminescence Materials

Three kinds of pyrazolines were designed and synthesized. Their structures were elucidated by IR, (HNMR)-H-1, MS, UV and elemental analysis. Their luminescent properties were determined, which indicated that they had strong blue fluorescent properties. One of them was designed to have good film formation. All the three kinds of pyrazolines can be used as blue organic electroluminescence materials (OELMs).

Application of CO_2-TPD in the Synthesis of Composite Oxides from Metal-Organic Precursors

CO2-TPD was demonstrated an effective way to investigate the phase formation during pyrolysis for the preparation of composite oxides using metal-organic molecules as precursors.Based on the CO2-TPD results, it was found that calcination condition had deep effect on the carbonate formation and the minimum firing temperature to acquire pure phase composite oxide.An optimized calcination schedule was then developed.