The reaction mechanisms between formaldehyde and MoOx(x = 1, 2, 3) have been studied thoroughly in this paper. Five reaction pathways were found in three reactions(reactions Ⅰ to Ⅲ) through studying the mechanisms o...The reaction mechanisms between formaldehyde and MoOx(x = 1, 2, 3) have been studied thoroughly in this paper. Five reaction pathways were found in three reactions(reactions Ⅰ to Ⅲ) through studying the mechanisms of MoOx(x = 1, 2, 3) catalyzing formaldehyde. Different products were obtained from three reactions. Of all three reactions, the barrier energy of Route ⅡA is the lowest(4.70 kcal/mol), which means in MoOx(x = 1, 2, 3), MoO2 has the best catalytic effect. Compared with other similar non-toxic treatments of formaldehyde, our barrier energy is the lowest. In this research, there was no good leaving group of the compound, so the mechanisms are addition reaction. We speculate that there must be an addition reaction to the more complex reactions to molybdenum oxides and aldehydes. As a chemical reagent for removing formaldehyde, it only absorbs formaldehyde and does not emit other toxic substances outward. Molybdenum oxides retain its original structures of the final products, which means it has excellent stability in the reaction of MoOx(x = 1, 2, 3) + HCHO. The mechanisms of all three reactions are addition reactions, but they are entirely different. As the number of oxygen atoms increases, the reaction mechanisms become simpler.展开更多
We propose the complicated catalytic mechanisms for the acetic acid molecule catalyzed by transition metal oxide MoO2 based on density functional theory calculations.The geometries and energetic values of all stationa...We propose the complicated catalytic mechanisms for the acetic acid molecule catalyzed by transition metal oxide MoO2 based on density functional theory calculations.The geometries and energetic values of all stationaries and transition states involved in the three different reaction pathways(ChannelsⅠ,ⅡandⅢ)are reported and analyzed.All reaction mechanisms are fully different from that of MoxOy catalyzing volatile organic compounds(VOCs)in previous studies.The completely new mechanisms catalyzed by MoO2 for acetic acid have been discovered for the first time.ChannelsⅠ(ⅠA andⅠB)andⅡare both addition reactions and channelⅢis hydrogen abstraction reaction by producing a leaving group.The barrier energies of reaction are also compared with other catalytic reactions,showing that MoO2 catalyst expresses a lower barrier energy(8.22 kcal/mol)by addition reaction,which represents MoO2 tends to absorb acetic acid pollution gas via addition reaction rather than release toxic substances.This also means that MoO2 is a more effective and representative catalyst and is suitable for further study of catalytic carboxylic acids,so the reaction mechanisms may provide a useful theoretical guidance and solution for the catalysis of carboxylic acids.展开更多
To search for potential energetic materials with large energy density and acceptable thermodynamics and kinetics stability,twelve derivatives of 4-nitro-5-(5-nitro-1,2,4-triazol-3-yl)-2H-1,2,3-triazolate(named A~L)are...To search for potential energetic materials with large energy density and acceptable thermodynamics and kinetics stability,twelve derivatives of 4-nitro-5-(5-nitro-1,2,4-triazol-3-yl)-2H-1,2,3-triazolate(named A~L)are designed and analyzed by using density functional theory(DFT)calculations at the B3LYP/6-311G**level of theory.The molecular heats of formation(HOF),electronic structures,impact sensitivity(H_(50)),oxygen balance(OB)and density(ρ)are investigated by isodesmic reaction method and physicochemical formulas.Furthermore,the detonation velocity(D)and detonation pressure(P)are calculated to study the detonation performance by Kamlet-Jacobs(K-J)equation.These results show that new molecule J(H_(50)=36.9 cm,ρ=1.90g/cm^(3),Q=1912.46 cal/g,P=37.82 GPa,D=9.22 km/s,OB=0.00),compound A(H_(50)=27.9 cm,ρ=1.93 g/cm^(3),Q=1612.93 cal/g,P=38.90 GPa,D=9.19 km/s)and compound H(H_(50)=37.3 cm,ρ=1.97 g/cm^(3),Q=1505.06cal/g,P=37.20 GPa,D=9.01 km/s)present promising effects that are far better RDX and HMX as the high energy density materials.Our calculations can provide useful information for the molecular synthesis of novel high energy density materials.展开更多
The geometric and electronic structures of the derivatives of 4-nitro-5-(5-nitroimino-1,2,4-triazol-3-yl)-2H-1,2,3-triazolate(named A~J)are explored employing density functional theory(DFT)calculations at the B3LYP/6-...The geometric and electronic structures of the derivatives of 4-nitro-5-(5-nitroimino-1,2,4-triazol-3-yl)-2H-1,2,3-triazolate(named A~J)are explored employing density functional theory(DFT)calculations at the B3LYP/6-311G^(**)level of theory.Based on the optimized molecular structures,the heats of formation(HOF)are obtained,and the electronic properties,density and molecular sensitivity by characteristic heights(H_(50))are discussed.Besides,the detonation performances(detonation velocity,detonation pressure)are estimated via Kamlet-Jacobs(K-J)formula.Compounds B(H50=29.4 cm,ρ=1.91 g/cm^(3),Q=1563.04 cal/g,P=36.05 GPa,D=8.95 km/s)and H(H_(50)=31.9 cm,ρ=1.80 g/cm^(3),Q=1610.09 cal/g,P=37.31 GPa,D=9.12 km/s)have positive HOFs and remarkable insensitivity and good detonation performance,strongly suggesting them as the acceptable new-type explosive.The initiating power surpasses conventional primary explosives,such as HMX.The outstanding detonation power of compounds B and H contributes to its future prospects as a promising green primary explosive.展开更多
基金supported by the school fund of Shanxi Institute of technology(201605001,20180010012)the 2016 annual major science and technology projects of Shanxi Province(MC2016-02/5)+2 种基金the Shanxi Advantageous and Characteristic Disciplines of “Project 1331”the National Natural Science Foundation of China(No.21373025)the major project of Tangshan Normal College(Nos.2017B01 and 2017B02)
文摘The reaction mechanisms between formaldehyde and MoOx(x = 1, 2, 3) have been studied thoroughly in this paper. Five reaction pathways were found in three reactions(reactions Ⅰ to Ⅲ) through studying the mechanisms of MoOx(x = 1, 2, 3) catalyzing formaldehyde. Different products were obtained from three reactions. Of all three reactions, the barrier energy of Route ⅡA is the lowest(4.70 kcal/mol), which means in MoOx(x = 1, 2, 3), MoO2 has the best catalytic effect. Compared with other similar non-toxic treatments of formaldehyde, our barrier energy is the lowest. In this research, there was no good leaving group of the compound, so the mechanisms are addition reaction. We speculate that there must be an addition reaction to the more complex reactions to molybdenum oxides and aldehydes. As a chemical reagent for removing formaldehyde, it only absorbs formaldehyde and does not emit other toxic substances outward. Molybdenum oxides retain its original structures of the final products, which means it has excellent stability in the reaction of MoOx(x = 1, 2, 3) + HCHO. The mechanisms of all three reactions are addition reactions, but they are entirely different. As the number of oxygen atoms increases, the reaction mechanisms become simpler.
基金Supported by the Shanxi Provincial Education Department(2019L0986)the 2016 annual major science and technology projects of Shanxi Province(MC2016-02/5)+4 种基金the Shanxi Advantageous and Characteristic Disciplines of“Project 1331”the school fund of Shanxi Institute of Technology(201605000120180010012 and 20190040013)the major project of Tangshan Normal College(Nos.2017B01 and B02)the 2019 abroad training project fund of Tangshan excellent young and middle-aged experts。
文摘We propose the complicated catalytic mechanisms for the acetic acid molecule catalyzed by transition metal oxide MoO2 based on density functional theory calculations.The geometries and energetic values of all stationaries and transition states involved in the three different reaction pathways(ChannelsⅠ,ⅡandⅢ)are reported and analyzed.All reaction mechanisms are fully different from that of MoxOy catalyzing volatile organic compounds(VOCs)in previous studies.The completely new mechanisms catalyzed by MoO2 for acetic acid have been discovered for the first time.ChannelsⅠ(ⅠA andⅠB)andⅡare both addition reactions and channelⅢis hydrogen abstraction reaction by producing a leaving group.The barrier energies of reaction are also compared with other catalytic reactions,showing that MoO2 catalyst expresses a lower barrier energy(8.22 kcal/mol)by addition reaction,which represents MoO2 tends to absorb acetic acid pollution gas via addition reaction rather than release toxic substances.This also means that MoO2 is a more effective and representative catalyst and is suitable for further study of catalytic carboxylic acids,so the reaction mechanisms may provide a useful theoretical guidance and solution for the catalysis of carboxylic acids.
基金Supported by theof Tangshan Normal University(2021B37and 2021B32)the School Fund of Shanxi Institute of Technology(2019004)the Fund of Shanxi Provincial Education Department(2019L0986)。
文摘To search for potential energetic materials with large energy density and acceptable thermodynamics and kinetics stability,twelve derivatives of 4-nitro-5-(5-nitro-1,2,4-triazol-3-yl)-2H-1,2,3-triazolate(named A~L)are designed and analyzed by using density functional theory(DFT)calculations at the B3LYP/6-311G**level of theory.The molecular heats of formation(HOF),electronic structures,impact sensitivity(H_(50)),oxygen balance(OB)and density(ρ)are investigated by isodesmic reaction method and physicochemical formulas.Furthermore,the detonation velocity(D)and detonation pressure(P)are calculated to study the detonation performance by Kamlet-Jacobs(K-J)equation.These results show that new molecule J(H_(50)=36.9 cm,ρ=1.90g/cm^(3),Q=1912.46 cal/g,P=37.82 GPa,D=9.22 km/s,OB=0.00),compound A(H_(50)=27.9 cm,ρ=1.93 g/cm^(3),Q=1612.93 cal/g,P=38.90 GPa,D=9.19 km/s)and compound H(H_(50)=37.3 cm,ρ=1.97 g/cm^(3),Q=1505.06cal/g,P=37.20 GPa,D=9.01 km/s)present promising effects that are far better RDX and HMX as the high energy density materials.Our calculations can provide useful information for the molecular synthesis of novel high energy density materials.
基金the of Tangshan Normal University(2021B37and 2021B32)the School Fund of Shanxi Institute of Technology(2019004)the Fund of Shanxi Provincial Education Department(2019L0986)。
文摘The geometric and electronic structures of the derivatives of 4-nitro-5-(5-nitroimino-1,2,4-triazol-3-yl)-2H-1,2,3-triazolate(named A~J)are explored employing density functional theory(DFT)calculations at the B3LYP/6-311G^(**)level of theory.Based on the optimized molecular structures,the heats of formation(HOF)are obtained,and the electronic properties,density and molecular sensitivity by characteristic heights(H_(50))are discussed.Besides,the detonation performances(detonation velocity,detonation pressure)are estimated via Kamlet-Jacobs(K-J)formula.Compounds B(H50=29.4 cm,ρ=1.91 g/cm^(3),Q=1563.04 cal/g,P=36.05 GPa,D=8.95 km/s)and H(H_(50)=31.9 cm,ρ=1.80 g/cm^(3),Q=1610.09 cal/g,P=37.31 GPa,D=9.12 km/s)have positive HOFs and remarkable insensitivity and good detonation performance,strongly suggesting them as the acceptable new-type explosive.The initiating power surpasses conventional primary explosives,such as HMX.The outstanding detonation power of compounds B and H contributes to its future prospects as a promising green primary explosive.
