Microwave-assisted Synthesis of Al_(4)SiC_(4) and Its Effect on Properties of MgO-C Refractories

Al_(4)SiC_(4) was synthesized from Al powder, silicon carbide, and graphite by microwave sintering, and characterized by XRD and SEM. Then the synthesized material was added to the magnesia carbon refractory brick to study its effect on the oxidation resistance, apparent porosity, bulk density, elastic modulus, and modulus of rupture. It is found that Al_(4)SiC_(4) can be synthesized by microwave sintering at 1 300 ℃ and the addition of Al_(4)SiC_(4)-containing material as an antioxidant can enhance the oxidation resistance of the magnesia carbon refractory brick.

Mass-Based Environmental Factor and Energy Assessment of Microwave-Assisted Synthesized Transition Metal Nanostructures

This paper describes mass-based energy phase-space projection of microwave-assisted synthesis of transition metals (zinc oxide, palladium, silver, platinum, and gold) nanostructures. The projection uses process energy budget (measured in kJ) on the horizontal axes and process density (measured in kJg−1) on the vertical axes. These two axes allow both mass usage efficiency (Environmental-Factor) and energy efficiency to be evaluated for a range of microwave applicator and metal synthesis. The metrics are allied to the: second, sixth and eleventh principle of the twelve principle of Green Chemistry. This analytical approach to microwave synthesis (widely considered as a useful Green Chemistry energy source) allows a quantified dynamic environmental quotient to be given to renewable plant-based biomass associated with the reduction of the metal precursors. Thus allowing a degree of quantification of claimed “eco-friendly” and “sustainable” synthesis with regard to waste production and energy usage.

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.

Microwave-Assisted Au and Ag Nanoparticle Synthesis: An Energy Phase-Space Projection Analysis

Microwave-assisted synthesis of gold and silver nanoparticles, as a function of Green Chemistry, non Green Chemistry, and four applicator types are reported. The applicator types are Domestic microwave ovens, commercial temperature controlled microwave chemistry ovens (TCMC), digesters, and axial field helical antennae. For each of these microwave applicators the process energy budget where estimated (Watts multiplied by process time = kJ) and energy density (applied energy divided by suspension volume = kJ·ml-1) range between 180 ± 176.8 kJ, and 79.5 ± 79 kJ·ml-1, respectively. The axial field helical field an-tenna applicator is found to be the most energy efficient (0.253 kJ·m-1 per kJ, at 36 W). Followed by microwave ovens (4.47 ± 3.9 kJ·ml-1 per 76.83 ± 39 kJ), and TCMC ovens (2.86 ± 2.3 kJ·m-1 per 343 ± 321.5 kJ). The digester applicators have the least energy efficiency (36.2 ± 50.7 kJ·m-1 per 1010 ± 620 kJ). A comparison with reconstructed ‘non-thermal’ microwave oven inactivation microorganism experiments yields a power-law signature of n = 0.846 (R2 = 0.7923) four orders of magnitude. The paper provides a discussion on the Au and Ag nanoparticle chemistry and bio-chemistry synthesis aspects of the microwave applicator energy datasets and variation within each dataset. The visual and analytical approach within the energy phase-space projection enables a nanoparticle synthesis route to be systematically characterized, and where changes to the synthesis are to be mapped and compared directly with historical datasets. In order to help identify lower cost nanoparticle synthesis, in addition to potentially reduce synthesis energy to routes informed changes to potentially reduce synthesis energy budget, along with nanoparticle morphology and yield.

Green Chemistry Allometry Test of Microwave-Assisted Synthesis of Transition Metal Nanostructures

Microwave irradiation is considered an important approach to Green Chemistry, because of its ability to rapidly increase the internal temperature of polar-organic compounds that lead to synthesis times of minutes rather than hours when compared to conventional thermal heating. This works describes a dual allometry test for the discrimination between the solvents and reagents used in the microwave-assisted synthesis of transition metal (zinc oxide, palladium silver, platinum, and gold) nanostructures. The test is performed in log-log process energy phase-space projection, where the synthesis data (kJ against kJ·mol-1) has a power-law signature. The test is shown to discriminate between recommended Green Chemistry, problematic Green Chemistry, and Green Chemistry hazardous solvents. Typically, recommended Green chemistry exhibits a broad y-axes distribution within an upper exponent = 1 and lower exponent = 0.5. Problematic Green Chemistry exhibits a y-axes narrower distribution with an upper exponent = 0.94 and lower exponent = 0.64. Non-Green Chemistry hazardous data exhibits a further narrowing of the y-axes distribution within upper exponent = 0.87 and lower exponent = 0.66. In all three cases, the y-axes is aligned to original database power-law signature. It is also shown that in the x-axes direction (process energy budget) the grouped order of magnitude decreases from four orders for recommended Green Chemistry solvent and reagent data, through two orders for non-Green Chemistry hazardous material and down to one order for problematic Green Chemistry.

Microwave-Assisted Transition Metal Nanostructure Synthesis: Power-Law Signature Verification

A power-law (y = cxn) signature between process energy budget (kJ) and process energy density (kJ·ml-1) of microwave-assisted synthesis of silver and gold nanostructures has been recently described [Law and Denis. AJAC, 14(4), 149-174, (2023)]. This study explores this relation further for palladium, platinum, and zinc oxide nanostructures. Parametric cluster analysis and statistical analysis is used to test the power-law signature of over four orders of magnitude as a function of six microwave applicator-types metal precursor, non-Green Chemistry synthesis and claimed Green Chemistry. It is found that for the claimed Green Chemistry, process energy budget ranges from 0.291 to 900 kJ, with a residual error ranging between −33 to +25.9 kJ·ml-1. The non-Green Chemistry synthesis has a higher process energy budget range from 3.2 kJ to 3.3 MJ, with a residual error of −33.3 to +245.3 kJ·ml-1. It is also found that the energy profile over time produced by software controlled digestion applicators is poorly reported which leads to residual error problematic outliers that produce possible phase-transition in the power-law signature. The original Au and Ag database and new Pd, Pt and ZnO database (with and without problematic outliers) yield a global microwave-assisted synthesis power-law signature constants of c = 0.7172 ± 0.3214 kJ·ml-1 at x-axes = 0.001 kJ, and the exponent, n = 0.791 ± 0.055. The information in this study is aimed to understand variations in historical microwave-assisted synthesis processes, and develop new scale-out synthesis through process intensification.

Microwave-assisted synthesis of asymmetric thiocarbonohydrazones under solvent-free conditions

Six new asymmetric thiocarbonohydrazones 3a-3f were synthesized from following steps： firstly hydrazine hydrate reacted with carbon disulfide to form thiocarbonohydrazide （1） under microwave irradiation. Then compound （1） reacted with ketone and different aldehydes step by step to give 3a-3f with excellent yields under solvent-free conditions using microwave irradiation. Their structures have been determined by elemental analysis, IR, MS and ^1H NMR data. 2009 Qing Han Li. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.

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.

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%.