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1.
研究了N2H4在间-四(邻-硝基苯基)四苯并卟啉铁(Ⅲ)、钴(Ⅱ)、锌(Ⅱ)和镍(Ⅱ)配合物[MTP(o-NO2)TBP,简称MTBP]修饰石墨电极上的催化电氧化反应,测得该系列金属四苯并卟啉的催化活性的顺序为Co(Ⅱ)TBP>ClFe(Ⅲ)TBP>Ni(Ⅱ)TBP>Zn(Ⅱ)TBP≈石墨,考察了Co(Ⅱ)TBP和ClFe(Ⅲ)TBP催化联氨电氧化反应的动力学过程.结果表明,OH-和N2H4在ClFe(Ⅱ)TBP修饰电极上的反应级数分别为2和1,而在Co(Ⅱ)TBP修饰电极上的均为1.根据电化学参数提出了可能的反应机理.  相似文献   

2.
梁晓琴  蒲雪梅  田安民 《化学学报》2010,68(16):1568-1576
采用密度泛函理论(DFT)方法在B3LYP/aug-cc-pvDZ理论水平上研究了CN, NO2, NH2, N3, N2H, NHNH2, N4H和N4H3等含氮取代基取代五嗪环上的氢原子生成的衍生物, 预测了它们的分子构型、分解能及含能性质. 对衍生物分解能的研究结果表明, CN和NH2取代的衍生物的分解能比未取代时更高, 而其余基团的取代使分解能降低; 取代基化合物的生成热越大, 取代五嗪中的氢原子后生成衍生物的生成热也越大. N4H3, NO2, H, N2H, N4H, N3和CN取代的五嗪衍生物的单位原子生成热为72.6~108.9 kJ, 比文献报道的三叠氮基-均三嗪的(70.2 kJ)更高. 对于CN, N2H, N4H3, N3和N4H取代的衍生物, 其生成热为871.4~1159.3 kJ•mol-1, 但N4H和N4H3的分解能较小, 稳定性较差. 因此, N3, N2H和CN取代的衍生物可能成为高能量、低感度的含能材料.  相似文献   

3.
355 nm光照下利用瞬态吸收光谱技术进行了有氧、无氧条件下二苯醚与亚硝酸体系的反应机理研究, 考察了其中瞬态物种的衰减行为, 并对其光解产物进行了GC-MS分析. 研究表明, HNO2在355 nm紫外光的照射下产生的OH自由基和二苯醚反应生成C12H10O-OH 加合物, N2条件下C12H10O-OH衰减的速率常数为(1.86±0.14)×105 s-1, 在有氧条件下, C12H10O-OH可转化为C12H10O-OHO2, 衰减的速率常数为(6.6±0.4)×106 s-1. N2条件下最终产物为苯酚、2-羟基二苯醚、4-羟基二苯醚、4-硝基二苯醚.  相似文献   

4.
用密度泛函方法B3LYP/6-311++G(d,p)和高级电子相关的偶合簇法CCSD(T)/6-311++G(d,p)研究了气相离子-分子反应B2H3-+CS2B2H3S-+CS的机理.结果表明,B2H3最可能进攻CS2中碳原子形成三元环中间体,随后通过氢迁移和最终消除CS的反应步骤形成硫原子转移产物H3BBS-+CS,反应大量放热且不需要活化能.B2H3直接对CS2中硫原子进攻夺取硫原子的反应方式存在一定能垒阻碍.计算结果有助于深入了解B2H3,B3H-6和B4H7-等缺电子硼氢负离子的反应行为.  相似文献   

5.
二氧化碳(CO2)不仅仅是一种温室气体,更是一种重要的、有效的碳一资源,其来源丰富、无毒、无污染、不易燃烧,可用于生产有机化学品、材料、糖类等.由于CO2分子中的碳处于最高氧化态,且其分子具有热力学和动力学惰性,因此人们不断探索新型反应途径,以及新型的催化体系来有效资源化利用CO2.近年来,利用各种不饱和烃类,在过渡金属催化剂协助下催化CO2与烯烃生成不饱和羧酸及其衍生物引起了极大关注.其中,催化CO2/C2H4耦合反应制备丙烯酸及其衍生物因其原子经济性而备受瞩目.以镍系催化体系为主的过渡金属催化CO2/C2H4偶联反应是CO2化学转化与高值利用非常重要的研究热点之一.综述了近年来CO2/C2H4偶联反应的最新进展,对相应的催化反应机理进行了评述.从多个角度对各位学者的研究进行分析比...  相似文献   

6.
具有五元环结构的偶氮化合物4,4-二甲基-4,5-二氢-3H-吡咯(N2C5H10),与Fe3(CO)12在甲苯中加热回流反应,生成双铁六羰基配合物Fe2(N2C5H10)(CO)6(1).反应中N=N双键被还原,配体以(N2C5H102-的形式与FeIFeI配位,形成具有蝶形结构的34e-化合物.研究了在脱羰基试剂Me3NO存在条件下,1和单齿膦配体PR3反应生成Fe2(N2C5H10)-(CO)5(PR3)(PR3=PPh3,2a;PCy3,2b)单取代配合物.光照条件下,化合物1中的CO配体还可以被双齿膦配体dppe[dppe=1,2-C2H4(PPh22]和dppbz[dppbz=1,2-C6H4(PPh22]取代,生成产物的类型和膦配体的夹角相关.与夹角较大的dppe反应,生成桥连产物Fe2(N2C5H10)(CO)4μ-dppe)(3a);而与刚性较大的dppbz反应时,Fe2(NR)2的蝶形结构打开呈四元环;其中一个Fe上的CO被取代,dppbz与该Fe中心螯合,生成具有桥连CO的化合物Fe2(N2C5H10)(μ-CO)(CO)4κ2-dppbz)(3b).合成具有FeI-CO-FeI结构的羰基化合物,一直是模拟[FeFe]氢化酶活性中心还原态结构Fe2(SR)2μ-CO)-(CO)5-xLx的重要挑战.该类Fe2(NR)2(CO)6-x(PR3x化合物的合成,能为探索模拟[FeFe]氢化酶活性中心结构提供新的途径和思路.以上化合物均通过核磁[31P(1H)NMR]、红外光谱(IR)、元素分析及X射线单晶结构衍射等表征.  相似文献   

7.
采用量子化学密度泛函理论(DFT)对NO与NHi自由基的反应机理进行了研究,并结合经典过渡态理论对各反应速率常数进行了计算。结果表明,NO与NH2自由基的反应体系可通过六个反应通道形成N2+H2O、N2O+H2和N2H+OH。从能量变化和反应速率两方面考虑,产物N2+H2O最容易生成,其最佳反应通道为NO+NH2→→N2+H2O;NO与NH自由基的反应体系可通过七个反应通道形成N2+OH、N2O+H和N2H+O;其中,N2+OH最容易生成,最佳反应通道为NO+NH→→N2+OH。比较发现, NH比NH2自由基更易与NO发生反应生成N2。因此,在实际运行中改变操作条件,实现NH2等向NH方向转化,有利于NOx的还原。  相似文献   

8.
根据原子价的量子化学定义,采用3-21G基组的ab initio方法,对B2H6及其桥原子取代物H4B2X2(X=F,Cl,OH,NH2,CH3)进行几何构型优化,讨论桥原子的成键特征,并计算了B4H10、B5H9和B5H11等硼氢化合物的原子价,讨论了它们的亲电和亲核取代反应活性。  相似文献   

9.
ClMe2SiSiMe2Cl顺序与茚基锂和环戊二烯基锂作用,生成(1-C9H7)Me2SiSiMe2C5H5.后者进一步与五羰基铁反应,得到硅硅桥联茚基环戊二烯基化合物[η55-(1-C9H6)Me2SiSiMe2C5H4]Fe2(CO)4 (2).化合物2在加热条件下发生重排反应,给出硅硅键和铁铁键复分解产物([-)Me2Si(η5-1-C9H6)Fe(CO)2SiMe2(η5-C5H4)Fe(CO)2(]-) (3).利用X射线衍射法,测定了2和3的分子结构.  相似文献   

10.
采用反应力场分子动力学(ReaxFF-MD)方法, 模拟了富燃料条件下乙烯在空气中的燃烧以及燃烧产生的自由基与氮气的相互作用. 采用ReacNetGenerator程序提取反应网络, 结合自编后处理程序确定反应网络上的相关反应, 分析了乙烯燃烧的反应路径, 以及自由基与N2的相关反应和NO的生成路径. 结果表明, 乙烯燃烧路径与已报道的通过乙烯燃烧反应机理模拟得到的燃烧路径一致, 说明用ReaxFF-MD方法模拟乙烯高温燃烧有效而可靠; 乙烯在富燃料条件下燃烧产生的CH, C2H, C2, C2O自由基是瞬发型NO生成的重要反应物. 这些自由基与N2的反应和NO的生成路径, 为构建乙烯和大分子碳氢燃料燃烧氮氧化物排放的反应机理提供了重要参考.  相似文献   

11.
采用量子化学计算方法研究了H2O2 氧化N2 生成N2O 和H2O 的机理.结果发现, H2O2 氧化N2 先通过1 个四元环过渡态形成中间体H2N2O2 分子,H2N2O2 再通过一个五元环过渡态形成N2O和H2O.根据计算得到的每步反应的活化能,得知H2O2 氧化N2 生成中间体H2N2O2 分子是整个反应的控制步骤.  相似文献   

12.
以N-(2-异丙酸)-邻羟基苯甲酰腙(C10H10N2O4, H3L)、2,6-吡啶二甲酸(2,6-H2PDA)与RE(NO3)3•nH2O (RE=Pr, Eu)在室温下反应, 合成了配合物1 [Pr2(H2L)2(HL)2(2,6-H2PDA)(H2O)2]•2H2O和配合物2 [Eu2(H2L)2(HL)2(2,6-H2PDA)- (H2O)2]•2H2O, 对其进行了元素分析、红外光谱、紫外光谱等表征, 测定了两种配合物的晶体结构. 通过紫外吸收光谱、荧光发射光谱和稳态荧光猝灭方法及其与溴化乙锭(EB)的竞争实验研究了两种配合物与小牛胸腺DNA的作用情况. 结果表明, 两种配合物与小牛胸腺DNA均是以插入方式结合的.  相似文献   

13.
该文报道了N,N′-(2-苯并咪唑基甲基)亚氨基甲基膦酸{bbimpH_2,[(C7H5N2)CH2]2NCH2PO3H2}的2个镍化合物Ni2(bbimp)2(4,4′-bipy)(H2O)2·2H2O(1)和[Ni2(bbimp)2(H2O)2][Ni(bbimp)(H2O)2]2·4H2O(2)。化合物1是4,4′-联吡啶作为桥连配体的中性双核结构。化合物2含有1个中性的[Ni2(bbimp)2(H2O)2]双核分子与2个中性的[Ni(bbimp)(H2O)2]单核分子。双核分子单元中的2个Ni!离子被2个膦酸氧桥连。在化合物2中,膦酸氧桥连的2个Ni!离子之间存在铁磁性相互作用。  相似文献   

14.
The structural and electronic characteristics of the Si2C2H2 and Si2C2 clusters are studied by ab initio calculations based on coupled cluster and density functional theory using the hybrid B3LYP functional. In addition, similar species, such as SiC2H2 and Si3C2H2, are also studied for comparison. It is illustrated that the lowest energy structures of all three hydrogenated clusters, which have the general form Si(n)(CH)2, n = 1, 2, 3, are fully analogous to the structures of the corresponding organometallic isovalent carboranes. The most stable structure of Si2C2H2 is obtained by attaching two hydrogens onto the carbon atoms of a higher energy (+1.5 eV) planar trapezoidal structure of Si2C2, followed by geometry optimization which leads to puckering of the planar structure. Furthermore, it is demonstrated that Si2C2H2 and the other two "similar" hydrogenated clusters are much more stable than the corresponding bare nonhydrogenated clusters. Comparison of Si2C2H2 and C2B2H4 shows that their structural and bonding similarity includes also nuclear rearrangement similarity. The two species are isomerizable with an energy difference between their lowest energy puckered 1,2- and 1,3-isomers of about +/-0.3 eV. It is suggested that SiC2H2, Si2C2H2, and Si3C2H2 are special cases of a larger class of stable clusters. It is speculated on the basis of the calculated infrared spectrum that Si2C2H2 and perhaps other members of this class of clusters could be found in appreciable abundance in interstellar space.  相似文献   

15.
The association reactions, C4H2(+) + C2H2 and C4H3(+) + C2H2 have been examined at pressures between 8 x 10(-8) and 1 x 10(-4) Torr at 298 K in an ion cyclotron resonance mass spectrometer. Association occurred via two different mechanisms. At pressures below approximately 2 x 10(-6) Torr, the association was bimolecular having rate coefficients k2 = 2.7 x 10(-10) cm3 s-1 and 2.0 x 10(-10) cm3 s-1 for C4H2+ and C4H3+, respectively. At pressures above approximately 2 x 10(-6) Torr, termolecular association was observed with rate coefficients, k3 = 5.7 x 10(-23) cm6 s-1 and 1.3 x 10(-23) cm6 s-1 for C4H2+ and C4H3+, respectively, when M = C2H2. The termolecular rate constants with N2, Ar, Ne, and He as the third body, M, are also reported. We propose that the low pressure bimolecular association process was the result of radiative stabilization of the complex and the termolecular association process was the result of collisional stabilization. Elementary rate coefficients were obtained and the lifetime of the collision complex was > or = 57 microseconds for (C6H4+)* and > or = 18 microseconds for (C6H5+)*. At pressures below 1 x 10(-6) Torr, approximately 11% of the (C6H4+)* were stabilized by photon emission and the remaining approximately 89% reverted back to reactants, while approximately 24% of the (C6H5+)* were stabilized by photon emission and the remaining approximately 76% reverted back to reactants. The ionic products of the C2H2(+) + C2H2 reaction, C4H2+ and C4H3+, were found to be formed with enough internal energy that they did not react by the radiative association channel until relaxed by several nonreactive collisions with the bath gas.  相似文献   

16.
吸附法脱除乙烯中少量氮气的研究   总被引:1,自引:0,他引:1  
采用重量法在电子天平上,研究了C2H4和N2单组分在5A、13X、丝光沸石和炭分子筛不同吸附剂上的吸附平衡性质和扩散动力学性质。单柱模拟变压吸附评价了炭分子筛吸附脱除C2H4-N2(N2为4.7%)混合组分中N2的性能,并对流速和压力的影响进行了考察。研究表明,该炭分子筛是吸附脱除C2H4中少量N2的理想吸附剂。  相似文献   

17.
2MgO·2B2O3·MgCl2·14H2O-7.8%H3BO3-H2O体系多温相关系研究   总被引:1,自引:0,他引:1  
研究了2MgO·2B2O3·MgCl2·14H20在不同温度下的7.8%H3BO3水溶液中的相转化产物及其溶解度.IR,XRD,TG及化学分析表明,相转化产物在0~22℃范围内为MgO·2B2O3·9H20;22~68℃为MgO·2B2O3·7.5H20;68~95℃为MgO·2B2O3·7H20;95~98.8℃为MgO·2B2O3·5H20;100~110℃为MgO·B2O3·3H20;110~120℃为2MgO·B2O3·2H20;120~170℃为2MgO·B2O3·1.5H20;170~200℃为2MgO·B2O3·H20.提出了相转化反应原理.  相似文献   

18.
The reactions of the trans-Fe(DMeOPrPE)2Cl2 complex (I; DMeOPrPE = 1,2-bis(bis(methoxypropyl)phosphino)ethane) and its derivatives were studied in aqueous and nonaqueous solvents with a particular emphasis on the binding and activation of H2 and N2. The results show there are distinct differences in the reaction pathways between aqueous and nonaqueous solvents. In water, I immediately reacts to form trans-Fe(DMeOPrPE)2(H2O)Cl+. Subsequent reaction with H2 or N2 yields trans-Fe(DMeOPrPE)2(X2)Cl+ (X2=H2 or N2). In the case of H2, further reactivity occurs to ultimately give the trans-Fe(DMeOPrPE)2(H2)H+ product (III). The pathway for the reaction I --> III was spectroscopically examined: following the initial loss of chloride and replacement with H2, heterolysis of the H2 ligand occurs to form Fe(DMeOPrPE)2(H)Cl; substitution of the remaining chloride ligand by another H2 molecule then occurs to produce trans-Fe(DMeOPrPE)2(H2)H+. In the absence of H2 or N2, trans-Fe(DMeOPrPE)2(H2O)Cl+ slowly reacts in water to form Fe(DMeOPrPE)32+, II. Experiments showed that this species forms by reaction of free DMeOPrPE ligand with trans-Fe(DMeOPrPE)2(H2O)Cl+, where the free DMeOPrPE ligand comes from dissociation from the trans-Fe(DMeOPrPE)2(H2O)Cl+ complex. In nonaqueous solvents, the chloride ligand in I is not labile, and a reaction with H2 only occurs if a chloride abstracting reagent is present. Complex III is a useful synthon for the formation of other water-soluble metal hydrides. For example, the trans-[Fe(DMeOPrPE)2H(N2)]+ complex was generated in H2O by substitution of N2 for the H2 ligand in III. The trans-Fe(DHBuPE)2HCl complex (DHBuPE = 1,2-bis(bis(hydroxybutyl)phosphino)ethane, another water-solubilizing phosphine) was shown to be a viable absorbent for the separation of N2 from CH4 in a pressure swing scheme. X-ray crystallographic analysis of II is the first crystal structure report of a homoleptic tris chelate of FeII containing bidentate phosphine ligands. The structure reveals severe steric crowding at the Fe center.  相似文献   

19.
Zheng YQ  Lin JL  Xu W  Xie HZ  Sun J  Wang XW 《Inorganic chemistry》2008,47(22):10280-10287
Seven new glutaric acid complexes, Co(H 2O) 5L 1, Na 2[CoL 2] 2, Na 2[L(H 2L) 4/2] 3, {[Co 3(H 2O) 6L 2](HL) 2}.4H 2O 4, {[Co 3(H 2O) 6L 2](HL) 2}.10H 2O 5, {[Co 3(H 2O) 6L 2]L 2/2}.4H 2O 6, and Na 2{[Co 3(H 2O) 2]L 8/2].6H 2O 7 were obtained and characterized by single-crystal X-ray diffraction methods along with elemental analyses, IR spectroscopic and magnetic measurements (for 1 and 2). The [Co(H 2O) 5L] complex molecules in 1 are assembled into a three-dimensional supramolecular architecture based on intermolecular hydrogen bonds. Compound 2 consists of the Na (+) cations and the necklace-like glutarato doubly bridged [ C o L 4 / 2 ] 2 - infinity 1 anionic chains, and 3 is composed of the Na (+) cations and the anionic hydrogen bonded ladder-like [ L ( H 2 L ) 4 / 2 ] 2 - infinity 1 anionic chains. The trinuclear {[Co 3(H 2O) 6L 2](HL) 2} complex molecules with edge-shared linear trioctahedral [Co 3(H 2O) 6L 2] (2+) cluster cores in 4 and 5 are hydrogen bonded into two-dimensional (2D) networks. The edge-shared linear trioctahedral [Co 3(H 2O) 6L 2] (2+) cluster cores in 6 are bridged by glutarato ligands to generate one-dimensional (1D) chains, which are then assembled via interchain hydrogen bonds into 2D supramolecular networks. The corner-shared linear [Co 3O 16] trioctahedra in 7 are quaternate bridged by glutarato ligands to form 1D band-like anionic {[Co 3(H 2O) 2]L 8/2} (2+) chains, which are assembled via interchain hydrogen bonds into 2D layers, and between them are sandwiched the Na (+) cations. The magnetic behaviors of 1 and 2 obey the Curie-Weiss law with chi m = C/( T - Theta) with the Curie constant C = 3.012(8) cm (3) x mol (-1) x K and the Weiss constant Theta = -9.4(7) K for 1, as well as C = 2.40(1) cm (3) x mol (-1) x K and Theta = -2.10(5) K for 2, indicating weak antiferromagnetic interactions between the Co(II) ions.  相似文献   

20.
曾亚超  武刚 《催化学报》2021,42(12):2149-2163
流行性疾病贯穿整个人类历史,伴随全球人口流动,它们可能演变成大型流行病.时至今日,我们仍在见证已知和新生的病原体对人类历史格局的改变.在与流行性疾病的抗争中,诸如紫外线辐射、巴氏杀菌和化学氧化法等技术被用于病原体的消杀和抗体的研制.然而,这些技术在环境消毒方面存在诸多不利,譬如过长的消杀时间、昂贵的特殊设备以及伴生的环境污染.过氧化氢是一种环境友好的多功能氧化剂,其分解的最终产物是氧气和水,广泛用于伤口消毒、纸浆和纺织品漂白、废水废气处理、化学合成、半导体清洗以及洗涤剂.目前,过氧化氢的生产严重依赖于传统的蒽醌法,该技术由Riedl和Pfleiderer于1939年提出,并沿用至今.然而,蒽醌法能耗高,该技术仅在较大规模上经济可行.不稳定的过氧化氢溶液存在危险性,这对大宗过氧化氢的运输和存储提出了额外的挑战.电化学合成过氧化氢被认为可有效替代传统蒽醌法,其反应条件温和,所需反应物是环境中广泛存在的水和氧气;与可再生能源相结合,有望实现分布式原位生产过氧化氢.过氧化氢既可以通过两电子的水氧化反应生成,又可以经由两电子的氧还原反应产生.Berl等在上世纪30年代首次报道了经由两电子的氧还原反应合成过氧化氢,并随后在1991年将其商业化(亦即Huron-Dow法).自此,Huron-Dow法被广泛用于纸浆和纸张的漂白过程.最近,Huron-Dow法进一步演变为电子-芬顿工艺,并被广泛用于饮用水净化和污水处理.目前,涉及高活性和高选择性的电化学合成过氧化氢的优秀综述见诸各大期刊;但是鲜有综述探讨该技术在环境消毒方面的应用.为了探寻提升公共卫生安全的有效替代方法,本文探讨了在电催化制备过氧化氢在环境消毒方面的可行性.本文涵盖三个主题,从基础理论到实践两个层次探讨了该技术在实际应用中的可行性.首先,回顾了H2O2消杀病原体的机理;其次,讨论了影响电催化制备过氧化氢的关键因素,并对现有的用于两电子水氧化和氧还原的催化剂进行了系统性的评述;最后,讨论了电极和电解池的合理设计,以实现电催化制备过氧化氢在实际中的应用.本文试图为最终实现电催化制备过氧化氢在环境消毒,尤其是公共卫生领域,提供可寻的研究方向.  相似文献   

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