Progress in Reaction Kinetics and Mechanism最新文献_第6页

Ab initio study of mechanism of forming a Si-heterocyclic spiro-Sn-heterocyclic ring compound by cycloaddition reaction of Me2Si=Sn: and ethene Me2Si=Sn:与乙烯的环加成反应生成si - spro -Sn-杂环化合物机理的从头算研究

IF 0.7 4区化学

Progress in Reaction Kinetics and Mechanism Pub Date : 2019-05-01 DOI: 10.1177/1468678319825898

Xiaojun Tan, Xiuhui Lu

{"title":"Ab initio study of mechanism of forming a Si-heterocyclic spiro-Sn-heterocyclic ring compound by cycloaddition reaction of Me2Si=Sn: and ethene","authors":"Xiaojun Tan, Xiuhui Lu","doi":"10.1177/1468678319825898","DOIUrl":"https://doi.org/10.1177/1468678319825898","url":null,"abstract":"X2Si=Sn: (X = H, Me, F, Cl, Br, Ph, Ar, etc.) are a new chemical species. The cycloaddition reactions of X2Si=Sn: are a new field of stannylene chemistry. The mechanism of the cycloaddition reaction between singlet state Me2Si=Sn: and ethene has been investigated for the first time here using second-order Møller-Plesset perturbation theory together with the 6-311++G** basis set for C, H and Si atoms and the LanL2dz basis set for Sn atoms. From the potential energy profile, it could be predicted that the reaction has one dominant reaction channel. The reaction process presented is that the 5p unoccupied orbital of Sn in Me2Si=Sn: and the π orbital of ethene form a π → p donor–acceptor bond resulting in the formation of an intermediate. The instability of this intermediate makes it isomerize to a four-membered Si-heterocyclic ring stannylene. Because the 5p unoccupied orbital of the Sn atom in the four-membered Si-heterocyclic ring stannylene and the π orbital of ethene form a π → p donor–acceptor bond, the four-membered Si-heterocyclic ring stannylene further combines with ethene to form another intermediate. Because the Sn atom in this intermediate assumes sp3 hybridization after the transition state, the intermediate isomerizes to a Si-heterocyclic spiro-Sn-heterocyclic ring compound. This result indicates the modes of cycloaddition reactions between X2Si=Sn: and symmetric π-bonded compounds, i.e. this study opens up a new field for stannylene chemistry.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":null,"pages":null},"PeriodicalIF":0.7,"publicationDate":"2019-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78878810","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A density functional theory study of the oxygen reduction reaction on the (111) and (100) surfaces of cobalt(II) oxide 氧化钴(II)(111)和(100)表面氧还原反应的密度泛函理论研究

IF 0.7 4区化学

Progress in Reaction Kinetics and Mechanism Pub Date : 2019-04-24 DOI: 10.1177/1468678319825727

B. Qin, Yang Tian, Pengxiang Zhang, Zuoyin Yang, Guoxin Zhang, Zhao Cai, Yaping Li

{"title":"A density functional theory study of the oxygen reduction reaction on the (111) and (100) surfaces of cobalt(II) oxide","authors":"B. Qin, Yang Tian, Pengxiang Zhang, Zuoyin Yang, Guoxin Zhang, Zhao Cai, Yaping Li","doi":"10.1177/1468678319825727","DOIUrl":"https://doi.org/10.1177/1468678319825727","url":null,"abstract":"Density functional theory calculations were employed to investigate the electrochemical oxygen reduction reaction on the (111) and (100) surfaces of cobalt(II) oxide. Different mechanisms were applied to evaluate the oxygen reduction reaction performance of cobalt(II) oxide structures in terms of the Gibbs free energy and density of states. A variety of intermediate structures based on associative and dissociative mechanisms were constructed and optimized. As a result, we estimated the catalytic activity by calculating the free energy of the intermediates and constructing free energy diagrams, which suggested that the oxygen reduction reaction Gibbs free energy on cobalt(II) oxide (111) and (100) surfaces based on the associative mechanism is smaller than that based on the dissociative mechanism, demonstrating that the associative mechanism should be more likely to be the oxygen reduction reaction pathway. Moreover, the theoretical oxygen reduction reaction activity on the cobalt(II) oxide (111) surface was found to be higher than that on the cobalt(II) oxide (100) surface. These results shed light on the rational design of high-performance cobalt(II) oxide oxygen reduction reaction catalysts.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":null,"pages":null},"PeriodicalIF":0.7,"publicationDate":"2019-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75035827","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 4

Pyrolysis and gasification of macroalgae Enteromorpha prolifera under a CO2 atmosphere using the thermogravimetry–Fourier transform infrared spectroscopy technique 利用热重-傅里叶变换红外光谱技术研究了大型藻浒苔在CO2气氛下的热解气化过程

IF 0.7 4区化学

Progress in Reaction Kinetics and Mechanism Pub Date : 2019-04-24 DOI: 10.1177/1468678319825735

Junrui Cao, Yuhui Ma

{"title":"Pyrolysis and gasification of macroalgae Enteromorpha prolifera under a CO2 atmosphere using the thermogravimetry–Fourier transform infrared spectroscopy technique","authors":"Junrui Cao, Yuhui Ma","doi":"10.1177/1468678319825735","DOIUrl":"https://doi.org/10.1177/1468678319825735","url":null,"abstract":"Non-isothermal pyrolysis and gasification of Enteromorpha prolifera (also known as Ulva prolifera) under a CO2 atmosphere were investigated by thermogravimetry analysis. The gaseous products were measured online with Fourier transform infrared spectroscopy coupled with thermogravimetry. The kinetic parameters of pyrolysis and gasification reactions were obtained using the Coats–Redfern method. The experimental results showed that Enteromorpha prolifera had two derivative thermogravimetry peaks centered at 240 and 800°C, indicating the pyrolysis of organics and gasification of char, respectively. Carboxylic acids, ethers, and alcohols were the dominating condensable products generated from pyrolysis between 230 and 300°C. H2O, CH4, and aliphatic hydrocarbons were also formed in this temperature range, and they were also continuously released at higher temperatures, indicating further polymerization of the freshly generated pyrolytic char. CO was mainly produced between 700 and 900°C, and its yield was much higher than that of the pyrolytic gaseous products. The Ginstling equation (the D4 model) proved to be the most probable mechanism function for both the pyrolysis and gasification stages, with activation energies of 138.30 and 93.43 kJ mol−1, respectively.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":null,"pages":null},"PeriodicalIF":0.7,"publicationDate":"2019-04-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83889899","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 8

Study on the reactions between dichlorido[2,2′:6′,2″-terpyridine] zinc(II) and biologically relevant nucleophiles in aqueous solution 二氯[2,2 ':6 '，2″-三吡啶]锌(II)与生物相关亲核试剂在水溶液中的反应研究

IF 0.7 4区化学

Progress in Reaction Kinetics and Mechanism Pub Date : 2019-04-22 DOI: 10.1177/1468678319825724

Enisa Selimović, T. Soldatović

引用次数: 1

Mechanistic and energetic studies of superparamagnetic iron oxide nanoparticles as a cyclophosphamide anticancer drug nanocarrier: A quantum mechanical approach 超顺磁性氧化铁纳米颗粒作为环磷酰胺抗癌药物纳米载体的机理和能量研究:量子力学方法

IF 0.7 4区化学

Progress in Reaction Kinetics and Mechanism Pub Date : 2019-04-10 DOI: 10.1177/1468678319825689

N. Mozayyeni, A. Morsali, M. Bozorgmehr, S. Beyramabadi

{"title":"Mechanistic and energetic studies of superparamagnetic iron oxide nanoparticles as a cyclophosphamide anticancer drug nanocarrier: A quantum mechanical approach","authors":"N. Mozayyeni, A. Morsali, M. Bozorgmehr, S. Beyramabadi","doi":"10.1177/1468678319825689","DOIUrl":"https://doi.org/10.1177/1468678319825689","url":null,"abstract":"Using Fe6(OH)18(H2O)6 as a ring cluster model for superparamagnetic iron oxide nanoparticles, noncovalent configurations and three mechanisms of covalent functionalization of superparamagnetic iron oxide nanoparticles with cyclophosphamide an anticancer drug were studied. Quantum molecular descriptors, solvation, and binding energies of noncovalent interactions were investigated the in gas and solution phases at the B3LYP and M06-2X density functional levels. In the vicinity of superparamagnetic iron oxide nanoparticles, the reactivity of the drug increases, showing cyclophosphamide can probably bind to superparamagnetic iron oxide nanoparticles through Cl (k1 mechanism), P=O (k2 mechanism), and NH in a six-membered ring (k3 mechanism) groups. The activation parameters of all pathways were calculated, indicating the high barriers related to the k1 and k2 mechanisms are higher the barrier related to the k3 mechanism. The k3 mechanism is also spontaneous and exothermic and is therefore the preferred mechanism for covalent functionalization.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":null,"pages":null},"PeriodicalIF":0.7,"publicationDate":"2019-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86890386","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Effect of Ti on dibenzothiophene hydrodesulfurization performance over bulk Ni2P 钛对二苯并噻吩在Ni2P上加氢脱硫性能的影响

IF 0.7 4区化学

Progress in Reaction Kinetics and Mechanism Pub Date : 2019-04-10 DOI: 10.1177/1468678319825693

C. Han, Hua Song, N. Jiang, Yanguang Chen, Feng Li, Tianzhen Hao

引用次数: 0

The effect of neodymium and yttrium on benzofuran hydrodeoxygenation performance over a bulk Ni2P catalyst 钕钇对Ni2P催化剂上苯并呋喃加氢脱氧性能的影响

IF 0.7 4区化学

Progress in Reaction Kinetics and Mechanism Pub Date : 2019-04-10 DOI: 10.1177/1468678319830488

Hua Song, Xueyan Dai, N. Jiang, Zijin Yan, Tianhan Zhu, Feng Li

引用次数: 1

Kinetic modeling of butane-2,3-diol dehydration over Nb2O5.nH2O 丁烷-2,3-二醇在Nb2O5.nH2O上脱水的动力学模拟

IF 0.7 4区化学

Progress in Reaction Kinetics and Mechanism Pub Date : 2019-04-10 DOI: 10.1177/1468678319825686

Guilin Cheng, Lin-yan Wang, Chengjun Jiang

引用次数: 2

Oxidation reaction mechanism and kinetics between OH radicals and alkyl-substituted aliphatic thiols: OH-addition pathways 羟基自由基与烷基取代脂肪族硫醇氧化反应机理及动力学:羟基加成途径

IF 0.7 4区化学

Progress in Reaction Kinetics and Mechanism Pub Date : 2019-03-26 DOI: 10.1177/1468678319832382

A. Tahan, A. Shiroudi

{"title":"Oxidation reaction mechanism and kinetics between OH radicals and alkyl-substituted aliphatic thiols: OH-addition pathways","authors":"A. Tahan, A. Shiroudi","doi":"10.1177/1468678319832382","DOIUrl":"https://doi.org/10.1177/1468678319832382","url":null,"abstract":"Kinetic rate constants for the oxidation reactions of OH radicals with CH3SH (1), C2H5SH (2), n-C3H7SH (3) and iso-C3H7SH (4) under inert conditions (Ar) over the temperature range 252−430 K have been studied using the CBS-QB3 composite method. Kinetic rate constants under atmospheric pressure and in the fall-off regime have been estimated using transition state theory (TST) and statistical Rice–Ramsperger–Kassel–Marcus (RRKM) theory. Comparison with experiment confirms that in the OH-addition pathways 1−4 leading to the related products, the first bimolecular reaction step has effective negative activation energies around −2.61 to 3.70 kcal mol−1. Effective rate coefficients have been calculated according to a steady-state analysis of a two-step model reaction mechanism. As a result of the negative activation energies, pressures larger than 104 bar would be required to restore to some extent the validity of this approximation for all the channels. By comparison with experimental data, all our calculations for both the OH-addition and H-abstraction reaction pathways indicate that from a kinetic viewpoint and in line with the computed reaction energy barriers, the most favourable process is the OH-addition pathway to n-C3H7SH to yield the [n-C3H7SH−OH]• species, whereas under thermodynamic control of the bimolecular reactions (R−SH+OH•), the most abundant product derived from the H-abstraction pathway will be the [n-C3H7 S•+H2O] species.","PeriodicalId":20859,"journal":{"name":"Progress in Reaction Kinetics and Mechanism","volume":null,"pages":null},"PeriodicalIF":0.7,"publicationDate":"2019-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90272888","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 2

Interaction of intermediates with transition metal surfaces in the dehydrogenation of ethanol to ethyl acetate: A theoretical investigation 乙醇脱氢制乙酸乙酯过程中中间体与过渡金属表面的相互作用:理论研究

IF 0.7 4区化学

Progress in Reaction Kinetics and Mechanism Pub Date : 2019-03-22 DOI: 10.1177/1468678319834831

Adel Boualouache, A. Boucenna, Ghazi Otmanine

引用次数: 4