Ming Lu

Find an error

Name: 陆明

Organization: Nanjing University of Science and Technology , China

Department: School of Chemical Engineering

Title: NULL(PhD)

Chemicals
References

3D-Cube Layer Stacking: A Promising Strategy for High-Performance Insensitive Energetic Materials

Co-reporter:Qi Sun, Cheng Shen, Xin Li, Qiuhan Lin, and Ming Lu

Crystal Growth & Design November 1, 2017 Volume 17(Issue 11) pp:6105-6105

Publication Date(Web):October 3, 2017

DOI:10.1021/acs.cgd.7b01264

It is desirable to consider the molecular design and crystal configuration in the research of energetic materials. We discovered an interesting layer stacking crystal configuration, which is different from previous 2D-plane layer stacking, and termed it as “3D-cube layer stacking”. This new configuration, resulting from the unusual U-shaped molecular structures and vast H-bonding interactions, breaks through the limitations of the planar molecular structures in 2D-plane layer stacking. Compound 4, which features such characteristics, exhibits excellent energetic performance (D: 9043 m s–1; P: 35.6 GPa) and acceptable sensitivities (IS: 16 J; FS: 180 N). These positive results indicate that 3D-cube layer stacking may open new avenues for the design of energetic materials.

Synthesis and characterization of the pentazolate anion cyclo-N5ˉ in (N5)6(H3O)3(NH4)4Cl

Co-reporter:Chong Zhang;Chengguo Sun;Bingcheng Hu;Chuanming Yu

Science 2017 Volume 355(Issue 6323) pp:374-376

Publication Date(Web):27 Jan 2017

DOI:10.1126/science.aah3840

A salty route to an all-nitrogen ring

The flip side of the robust stability of N₂ is the instability of any larger molecules composed exclusively of nitrogen. These molecules nonetheless remain enticing targets for explosive and propellant applications. Zhang et al. successfully prepared the pentazolate ion, a negatively charged ring of five nitrogens, by oxidative cleavage of a C–N bond in an aryl-substituted precursor (see the Perspective by Christe). The molecule was stabilized and isolated in the solid state as a hydrated ammonium chloride salt. Spectroscopic and crystallographic characterization confirmed the ring's planar geometry.

Science, this issue p. 374; see also p. 351

Self-assembly of silver(I)-based high-energy metal–organic frameworks (HE-MOFs) at ambient temperature and pressure: synthesis, structure and superior explosive performance

Co-reporter:Cheng Shen;Yang Liu;Zhong-qin Zhu;Yuan-gang Xu

Chemical Communications 2017 vol. 53(Issue 54) pp:7489-7492

Publication Date(Web):2017/07/04

DOI:10.1039/C7CC03869K

Two new high-energy metal–organic frameworks (HE-MOFs), {Ag2(DNMAF)(H2O)2}n (1) and {Ag2(DNMAF)}n (2) were prepared using potassium 4,4′-bis(dinitromethyl)-3,3′-azofurazanate (K2DNMAF) in a self-assembly strategy. Compound 1 exhibits a 3D HE-MOF structure with coordinated water molecules. Compound 2 exhibits compact solvent-free 3D HE-MOFs. Both compounds show good thermostability (decomposition temperature (Td) of 211 and 218 °C) and superior detonation velocities (D) of 9673 m s−1 and 10 242 m s−1, detonation pressures (P) of 50.01 GPa and 58.30 GPa, and heat of detonation (Q) of 1.95 kcal g−1 and 2.19 kcal g−1, respectively, which are even higher than those of RDX and HMX.

In situ synthesized 3D metal–organic frameworks (MOFs) constructed from transition metal cations and tetrazole derivatives: a family of insensitive energetic materials

Co-reporter:Yuangang Xu;Wei Liu;Dongxue Li;Houhe Chen

Dalton Transactions 2017 vol. 46(Issue 33) pp:11046-11052

Publication Date(Web):2017/08/22

DOI:10.1039/C7DT02582C

The combination of the hydrothermal method with in situ synthesis has been successfully employed to prepare a family of tetrazole-based energetic metal–organic frameworks (EMOFs) ([Ag(Mtta)]n, 1; [Cd5(Mtta)9]n, 2; [Pb3(bta)2(O)2(H2O)]n, 3; and [Pb(tztr)2(H2O)]n, 4) through [2 + 3] cycloaddition of azide anions and nitrile groups. All the synthesized EMOFs were characterized by single crystal X-ray diffraction, IR spectroscopy, elemental analysis (EA), different scanning calorimetry (DSC), and thermogravimetry (TG). Both complexes 1 and 4 consist of reticular two-dimensional (2D) layers that are linked by π–π overlap interactions between the ligands in neighbouring layers to form 3D supramolecular structures. In contrast, complexes 2 and 3 are 3D frameworks. The in situ formation of ligands bta and tztr has been described for the first time. Remarkably, thermogravimetric measurements demonstrated that the EMOFs 1–4 possess excellent thermostabilities with high decomposition temperatures up to 354, 389, and 372 °C for 1, 2, and 4, respectively. Sensitivity tests revealed that all the EMOFs are extremely insensitive.

A series of high-energy coordination polymers with 3,6-bis(4-nitroamino-1,2,5-oxadiazol-3-yl)-1,4,2,5-dioxadiazine, a ligand with multi-coordination sites, high oxygen content and detonation performance: syntheses, structures, and performance

Co-reporter:Cheng Shen;Yuan-gang Xu

Journal of Materials Chemistry A 2017 vol. 5(Issue 35) pp:18854-18861

Publication Date(Web):2017/09/12

DOI:10.1039/C7TA05479C

In this study, 3,6-bis(4-nitroamino-1,2,5-oxadiazol-3-yl)-1,4,2,5-dioxadiazine (H2BNOD), with a relatively high oxygen content (37.41%) and good detonation performance (density = 1.817 g cm−3, detonation velocity = 8490 m s−1), is used to prepare three new high-energy coordination polymers (CPs), {Ag2(BNOD)(DMF)2}n (1), {Ag2(BNOD)}n (1a), and {Cu(BNOD)(H2O)6}n (2), and a metal salt, Co(BNOD)(H2O)6 (3). Crystal structure analyses indicated that 1 is a 2D energetic coordination polymer (E-CP) with a three-dimensional wavy layer structure; 1a is a compact 3D E-CP without any solvent molecules. 2 exhibits a zigzag 1D chain structure, while the ionic salt 3 has a layer-by-layer structure (0D). Thermal analysis indicated that 1 and 1a exhibit good, as well as similar, thermostability (200 °C) owing to their compact framework structures. The enthalpy of formation is calculated from the constant-volume combustion energy. The four compounds exhibit detonation velocities (D) ranging from 7141 to 10 084 m s−1, detonation pressures (P) ranging from 25.10 to 58.04 GPa, and heat of detonation (Q) values from 1.11 to 1.91 kcal g−1. The impact sensitivities of the energetic salts were between 5 and 12 J, and their friction sensitivities ranged from 120 to 180 N, at the same level as those of RDX and HMX. Among these four compounds, 1a exhibits outstanding performance (D = 10 084 m s−1, P = 58.04 GPa and Q = 1.91 kcal g−1) with a compact 3D CP structure.

Combination of four oxadiazole rings for the generation of energetic materials with high detonation performance, low sensitivity and excellent thermal stability

Co-reporter:Qi Sun;Cheng Shen;Xin Li;Qiuhan Lin

Journal of Materials Chemistry A 2017 vol. 5(Issue 22) pp:11063-11070

Publication Date(Web):2017/06/06

DOI:10.1039/C7TA02209C

Energetic materials, which are comprised of four oxadiazole rings and linked by three different bridges ([–NH–NH–], [–NN–], and [–NN(O)–]) are developed. All synthesized compounds were fully characterized and five of them were further determined by single-crystal X-ray diffraction. As supported by X-ray data, closed packing and extensive hydrogen-bonding interactions result in high density, low sensitivity, and excellent thermal stability. It is worth pointing out that the [–NN–] compound 3 has a decomposition temperature of 322 °C, which, to our knowledge, is the highest known value for all compounds consisting of 1,2,4- and 1,2,5-oxadiazole rings. Dihydrazinium salt 14 exhibits excellent detonation performance (D = 9042 m s−1, P = 35.0 GPa, and IS > 40 J), superior even to RDX. This novel design strategy, which combines four oxadiazole rings into one molecule, promises a fine balance between high detonation performance and low sensitivity and opens a new chapter in oxadiazole chemistry.

A Green and Effective Approach of Two-Step 2,2′,4,4′,6,6′-Hexanitrostilbene Preparation and Its Industrial Scale Study

Co-reporter:Pengcheng Wang, Ting-ting Lu, and Ming Lu

Organic Process Research & Development 2016 Volume 20(Issue 3) pp:668-674

Publication Date(Web):February 18, 2016

DOI:10.1021/acs.oprd.5b00422

An environmental friendly approach for two-step synthesis of hexanitrostilbene (HNS) has been studied here. In the first step from trinitrotoluene (TNT) to hexanitrobienzyl (HNBB), commercial NaClO was employed as oxidant in mixed solvent of ethyl acetate/ethanol (0.25 mL/1.25 mL per mmol of TNT) instead of benzene/ethanol. In the second step from HNBB to HNS, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)/FeCl2 was used as an effective catalytic system with O2 in DMSO solvent. A complex of metal ion and O2 [M(n+1)OO•] was supposed to be the active agent, and TEMPO itself was difficult to initiate dehydrogenation of HNBB but could promote the catalytic cycle of complex M(n+1)OO•. Finally, we increased the scale from 30 to 1000 g to investigate the feasibility of production. The total yield of two steps would be unprecedentedly as high as 70%.

Bronsted acidic ionic liquid [C3SO3HDoim]HSO4 catalyzed one-pot three-component Biginelli-type reaction: An efficient and solvent-free synthesis of pyrimidinone derivatives and its mechanistic study

Co-reporter:Zhi-Lei Zhou, Peng-Cheng Wang, Ming Lu

Chinese Chemical Letters 2016 Volume 27(Issue 2) pp:226-230

Publication Date(Web):February 2016

DOI:10.1016/j.cclet.2015.10.010

A series of Bronsted acidic ionic liquids (ILs) were prepared and used for Biginelli-type condensation reaction among aromatic aldehydes, urea or thiourea and cyclopentanone. Through this reaction, the synthesis of various pyrimidinones could be achieved. Of interest, it was found that the reaction was efficiently catalyzed by a novel, eco-friendly functionalized IL [C3SO3HDoim]HSO4, which could be reused for at least 7 times without significantly loss of catalytic activity. The reaction proceeded efficiently at 80 °C to afford the desired products in good yield (up to 96%). In addition, a possible mechanism that accounted for the IL [C3SO3HDoim]HSO4-catalyzed reaction was proposed.A novel functionalized Bronsted acidic ionic liquid [C3SO3HDoim]HSO4 was synthesized and characterized by IR, 1H NMR, 13C NMR and LC/MS. In this ionic liquid, Biginelli-type condensation reaction of aromatic aldehydes, urea or thiourea and cyclopentanone was carried out and a mechanism of the reaction was also proposed.

Study on the one-pot oxidative esterification of glycerol with MOF supported polyoxometalates as catalyst

Co-reporter:Jie Zhu, Peng-cheng Wang and Ming Lu

Catalysis Science & Technology 2015 vol. 5(Issue 6) pp:3383-3393

Publication Date(Web):21 Apr 2015

DOI:10.1039/C5CY00102A

In this work, glycerol was treated under green and mild conditions (water solvent, H2O2 oxidant, 40 °C) in an attempt to utilise its additional value. With a metal organic framework (MOF) supported polyoxometallate (POM) as a catalyst, esters were generated as one of the major products which could be useful for various industrial applications. The selectivity of esters formation reached 34.5% in this one-pot oxidative esterification process. Benefiting from the pore limitation effect of the MOF, diffusion was restricted and the original products could be further transformed into esters with the existence of the POM. No other reagents were needed during this process, and all of the intermediates were produced from glycerol itself. The oxidative esterification reaction was studied in detail including the role of the MOF, the influence of pH and the POM type, the mechanism and so on. It was concluded that the POM served as the active site for this oxidative esterification process and H2O2 provided weak acidity in addition to the source of oxygen. Too stronger acidity and oxidizability were unfavourable to the generation of esters. Also, the catalysts could be recovered after reaction, exhibiting good stability and reusability.

Molecular Design and Property Prediction for a Series of Novel Dicyclic Cyclotrimethylene Trinitramines (RDX) Derivatized as High Energy Density Materials

Co-reporter:Cheng Shen, Pengcheng Wang, and Ming Lu

The Journal of Physical Chemistry A 2015 Volume 119(Issue 29) pp:8250-8255

Publication Date(Web):July 1, 2015

DOI:10.1021/acs.jpca.5b04969

Quantum chemistry calculations and thermodynamics methods were carried out to screen out novel high energy density materials (HEDMs) from several new derivatives with dicyclic structures of Cyclotrimethylene trinitramine (RDX). Their volumes, densities, heats of formation, detonation properties and impact sensitivities have been calculated with thermodynamics methods under DFT B3LYP 6-31++g (d, p) level and all of these compounds exhibit good performance as HEDMs. Especially, R4 has given outstanding values as a potential HEDM. Its crystal density (2.07 g/cm3), heat of detonation (1.67 kJ/g), detonation velocity (10051m/s), and detonation pressure (48.5 GPa) are even higher than those of CL-20 while its impact sensitivity (h50, 16 cm) remains a relative safety value. The results indicate that the derivative work in common explosives is a good strategy which can design novel HEDMs with high energetic properties and low sensitivity. And furthermore, some mature processes can be used to synthesize them.

The importance of molecular conformation to the properties: a DFT study of the polynitro heterocyclic compounds based on dodecahydrodiimidazo [4,5-b:4′,5′-e]pyrazine structure

Co-reporter:Qin Hua Li;Peng Cheng Wang

Structural Chemistry 2015 Volume 26( Issue 3) pp:667-674

Publication Date(Web):2015 June

DOI:10.1007/s11224-014-0524-1

Two series of polynitro heterocyclic compounds with three conformations are designed based on the obtained dodecahydrodiimidazo [4,5-b:4′,5′-e]pyrazine “565” structure. First, the conformations including boat, chair, and plane, are optimized at B3PW91/6-311+G(d,p) level and some important properties are calculated. Based on the bond order, bond dissociation enthalpies and molecular energy analysis, it is found that the boat conformation owns lower energy and better bond order than the other two, and thus is most stable. Then, a further study on the electrical potential surfaces (EPS) proves that the stability of boat conformation can be contributed to the better balance between the positive and negative EPS. Next, according to molecular energy gap and density of state, the effect of each group on molecule is investigated: electrons on nitro group, compared with those on the framework, are easier to be activated so as to cause decomposition, thus nitro groups will determine the stability of molecule. Finally, the explosive velocity, pressure, and impact sensitivity of designed compounds are calculated. Results show that their explosive performances are significantly better than current energetic materials, and it is extraordinary enough that some compounds among them also maintain very good sensitivity.

Polyoxometalate-Based MetalOrganic Frameworks as Catalysts for the Selective Oxidation of Alcohols in Micellar Systems

Co-reporter:Jie Zhu;Meng-nan Shen;Xue-jing Zhao;Peng-cheng Wang ; Ming Lu

ChemPlusChem 2014 Volume 79( Issue 6) pp:872-878

Publication Date(Web):

DOI:10.1002/cplu.201400009

Abstract

A series of nanosized metal–organic frameworks (MOFs) encapsulating different polyoxometalates (POMs) including H₃PW₄O₁₂, H₅PMo₁₂O₄₀, H₅PVMo₁₀O₄₀, H₅PV₂Mo₁₀O₄₀, and H₅PV₃Mo₁₀O₄₀ was synthesized and used in the selective oxidation of alcohols. The catalyst with a uniform size and morphology offered easy accessibility between substrates and catalyst. At the same time, the MOF ensured that the POM was encapsulated, which could dramatically prevent the assembly of the catalyst. Furthermore, the catalyst showed clear chemoselectivity, which was related to the size or accessibility of the substrates for surface pores. With cetyltrimethyl ammonium bromide aqueous solution as solvent, both improved reaction efficiency and simple recycling of the catalytic system were achieved to afford a green oxidation process.

Preparation of heteropoly acid based amphiphilic salts supported by nano oxides and their catalytic performance in the nitration of aromatics

Co-reporter:Peng-cheng Wang, Kai Yao and Ming Lu

RSC Advances 2013 vol. 3(Issue 7) pp:2197-2202

Publication Date(Web):18 Dec 2012

DOI:10.1039/C2RA21582A

A series of Keggin heteropoly acid anion based amphiphilic salts supported by nano oxides were synthesized and used as catalysts in the nitration of aromatic compounds with HNO3. The reaction conditions in the nitration of toluene were optimized and both 92.6% conversion and good para selectivity (ortho:para = 1.09) were obtained.

Regioselective Nitration of Aromatics with Nanomagnetic Solid Superacid SO42/ZrO2-MxOy-Fe3O4 and Its Theoretical Studies

Co-reporter:Peng Cheng Wang;Jie Zhu;Xiang Liu;Ting Ting Lu ; Ming Lu

ChemPlusChem 2013 Volume 78( Issue 4) pp:310-317

Publication Date(Web):

DOI:10.1002/cplu.201300001

Abstract

A series of micro- and nanosulfated zirconia loaded on Fe₃O₄ or other metal oxides (SO₄²⁻/ZrO₂-M_xO_y-Fe₃O₄ (M=Ti⁴⁺, V⁵⁺, and Zn²⁺)) was prepared, characterized, and used in nitration. The nitration conditions with these solid superacids were then optimized to achieve the best regioselectivity and improve the performances of the catalysts as well. In the experimental results, SZTF (SO₄²⁻/ZrO₂-TiO₂-Fe₃O₄) showed excellent catalytic activity and it increased the surface area of SO₄²⁻/ZrO₂ by up to 15 %. The increase not only facilitated the generation of NO₂⁺, but also provided more opportunities for metal ions to interact with aromatic compounds. With chlorobenzene as substrate, theoretical research on its geometric parameters, electron clouds, and electron spin density was used to investigate the interaction between transition metals and chlorobenzene.

Synthesis of novel magnetic chitosan supported protonated peroxotungstate and its catalytic performance for oxidation

Co-reporter:Jie Zhu, Peng Cheng Wang and Ming Lu

New Journal of Chemistry 2012 vol. 36(Issue 12) pp:2587-2592

Publication Date(Web):03 Oct 2012

DOI:10.1039/C2NJ40753A

A novel magnetically recoverable catalyst in which protonated peroxotungstate was immobilized into a network of cross-linked chitosan with a superparamagnetic Fe3O4 core (Fe3O4–CS/HWO) was prepared, characterized and used in oxidation reactions. With H2O2 as oxidant, a wide range of substrates including olefins, sulfides, amines and allylic alcohols could be oxidized selectively, exhibiting a relatively high utilization percentage of H2O2. Due to the existence of peroxotungstate as well as the magnetic core, both improved catalytic performance and facilitated separation were achieved for the reaction process.

Regioselectivity nitration of aromatics with N2O5 in PEG-based dicationic ionic liquid

Co-reporter:Peng-Cheng Wang, Ming Lu

Tetrahedron Letters 2011 Volume 52(Issue 13) pp:1452-1455

Publication Date(Web):30 March 2011

DOI:10.1016/j.tetlet.2011.01.053

Regioselective mononitration of simple aromatic compounds has been investigated with N2O5 as nitrating agent and a new PEG200-based dicationic acidic ionic liquid (PEG200-DAIL) as catalyst. The results of experiments show that this nitration system can significantly improve the para-selectivity of alkyl-benzenes and the ortho-selectivity of halogenated-benzenes. The PEG200-DAIL exhibits recyclable temperature-dependant phase behavior in CCl4 solvent, and it can be recycled without apparent loss of catalytic activity, and only 5% loss of weight is observed after six times recycling.

Selective oxidation of benzyl alcohol under solvent-free condition with gold nanoparticles encapsulated in metal-organic framework

Co-reporter:Jie Zhu, Peng Cheng Wang, Ming Lu

Applied Catalysis A: General (5 May 2014) Volume 477() pp:125-131

Publication Date(Web):5 May 2014

DOI:10.1016/j.apcata.2014.03.013

Self-assembly of silver(I)-based high-energy metal–organic frameworks (HE-MOFs) at ambient temperature and pressure: synthesis, structure and superior explosive performance

Co-reporter:Cheng Shen, Yang Liu, Zhong-qin Zhu, Yuan-gang Xu and Ming Lu

Chemical Communications 2017 - vol. 53(Issue 54) pp:NaN7492-7492

Publication Date(Web):2017/06/13

DOI:10.1039/C7CC03869K

Two new high-energy metal–organic frameworks (HE-MOFs), {Ag2(DNMAF)(H2O)2}n (1) and {Ag2(DNMAF)}n (2) were prepared using potassium 4,4′-bis(dinitromethyl)-3,3′-azofurazanate (K2DNMAF) in a self-assembly strategy. Compound 1 exhibits a 3D HE-MOF structure with coordinated water molecules. Compound 2 exhibits compact solvent-free 3D HE-MOFs. Both compounds show good thermostability (decomposition temperature (Td) of 211 and 218 °C) and superior detonation velocities (D) of 9673 m s−1 and 10242 m s−1, detonation pressures (P) of 50.01 GPa and 58.30 GPa, and heat of detonation (Q) of 1.95 kcal g−1 and 2.19 kcal g−1, respectively, which are even higher than those of RDX and HMX.

Study on the one-pot oxidative esterification of glycerol with MOF supported polyoxometalates as catalyst

Co-reporter:Jie Zhu, Peng-cheng Wang and Ming Lu

Catalysis Science & Technology (2011-Present) 2015 - vol. 5(Issue 6) pp:NaN3393-3393

Publication Date(Web):2015/04/21

DOI:10.1039/C5CY00102A

Combination of four oxadiazole rings for the generation of energetic materials with high detonation performance, low sensitivity and excellent thermal stability

Co-reporter:Qi Sun, Cheng Shen, Xin Li, Qiuhan Lin and Ming Lu

Journal of Materials Chemistry A 2017 - vol. 5(Issue 22) pp:NaN11070-11070

Publication Date(Web):2017/05/02

DOI:10.1039/C7TA02209C