{"currentpage":1,"firstResult":0,"maxresult":10,"pagecode":5,"pageindex":{"endPagecode":2,"startPagecode":1},"records":[{"abstractinfo":"采用<span style=\"color:red\">ONIOM</span>法研究了分子筛上噻吩的裂解反应,考察了分子筛骨架环境对反应巾各物种的几何构型、电荷分布以及整个反应的影响.比较了B3LYP和M05-2X泛函的计算结果.结果表明,分子筛骨架可很好地稳定反应带电中间体.促进了吸附分子的电荷分离,从而使反应活化能降低.与现在应用广泛的B3LYP泛函相比,最近开发的M05-2X泛函能够更准确地描述反应物分子和分子筛骨架的相互作用,计算得到的电荷分布和活化能也更为合理.整个反应的决速步是亲电取代反应,其活化能为122.4kJ/mol,随后的C-S键解离活化能较低,为75.5kJ/mol.","authors":[{"authorName":"李焱","id":"c2f39b63-2689-47be-856f-e34942ddc5f5","originalAuthorName":"李焱"},{"authorName":"郭文平","id":"5cabfba4-29f5-44df-a642-38bcb241e17a","originalAuthorName":"郭文平"},{"authorName":"樊卫斌","id":"79cc12be-4440-4c92-b837-955629906e58","originalAuthorName":"樊卫斌"},{"authorName":"秦张峰","id":"ded595f0-074b-452b-8954-69f1bc2b8dc2","originalAuthorName":"秦张峰"},{"authorName":"王建国","id":"bee346f6-639f-418e-b83b-16a65329695e","originalAuthorName":"王建国"}],"doi":"10.1016/S1872-2067(10)60126-X","fpage":"1419","id":"2298349c-eea7-490a-8da3-1552a77a51cf","issue":"12","journal":{"abbrevTitle":"CHXB","coverImgSrc":"journal/img/cover/CHXB.jpg","id":"18","issnPpub":"0253-9837","publisherId":"CHXB","title":"催化学报   "},"keywords":[{"id":"f245cde4-9a82-4265-8775-507ecd8d63e5","keyword":"<span style=\"color:red\">ONIOM</span>","originalKeyword":"ONIOM"},{"id":"d4ac85f7-4462-4307-a6bb-87904c73c50a","keyword":"M05-2X","originalKeyword":"M05-2X"},{"id":"3a010c23-4eb6-4399-afdf-dc0551dbda29","keyword":"分子筛骨架","originalKeyword":"分子筛骨架"},{"id":"5e7d5a5e-2326-4702-abdb-1661aea63f2c","keyword":"噻吩裂解","originalKeyword":"噻吩裂解"},{"id":"2a37201f-e6e5-44cf-b40e-2da0acf85f83","keyword":"密度泛函","originalKeyword":"密度泛函"}],"language":"zh","publisherId":"cuihuaxb201012001","title":"<span style=\"color:red\">ONIOM</span>法研究分子筛骨架对噻吩裂解反应的影响","volume":"31","year":"2010"},{"abstractinfo":"采用量子化学方法(<span style=\"color:red\">ONIOM</span>,B3LYP/6-31G(d,p):HF/3-21G)研究了锂型丝光沸石(LiMOR)的结构及其对胺类分子的吸附性能.在校正基组迭加误差的基础上计算得到氨、甲胺、二甲胺和三甲胺分子的吸附热分别为117.6,132.7,122.2和106.0kJ/mol,表明胺分子在LiMOR分子筛上吸附强度的次序为三甲胺＜氨＜二甲胺＜甲胺.通过结构优化得到了吸附复合物的平衡几何参数、电子结构数据以及N-H键伸缩振动频率,胺分子与分子筛之间的主要作用力为氮上的孤对电子和锂离子之间的静电作用力,胺分子与分子筛骨架氧之间的弱氢键作用对其吸附有一定的稳定作用.","authors":[{"authorName":"蒋南","id":"1ece1805-fa19-4856-9367-49ab7db5bd50","originalAuthorName":"蒋南"},{"authorName":"袁淑萍","id":"e67bc9db-27d6-43cf-bbb9-acb2e66a0920","originalAuthorName":"袁淑萍"},{"authorName":"秦张峰","id":"0e5b64b9-8fcb-40ac-b796-4f483e297d7c","originalAuthorName":"秦张峰"},{"authorName":"王建国","id":"0a13279b-e1dc-4fca-ad69-fb1dcb5df2b8","originalAuthorName":"王建国"},{"authorName":"焦海军","id":"b8172673-0276-479d-9eee-2fc58122cede","originalAuthorName":"焦海军"},{"authorName":"李永旺","id":"1e6675fa-9e47-45eb-8c6a-07910a92d66d","originalAuthorName":"李永旺"}],"doi":"","fpage":"779","id":"6551c1ae-d174-45b5-a78c-a41c3bd455af","issue":"10","journal":{"abbrevTitle":"CHXB","coverImgSrc":"journal/img/cover/CHXB.jpg","id":"18","issnPpub":"0253-9837","publisherId":"CHXB","title":"催化学报   "},"keywords":[{"id":"b76527b3-5d05-4b8f-8a20-be2a56ada5d2","keyword":"胺","originalKeyword":"胺"},{"id":"2542c2b5-20ff-47cd-a5a5-d822d77e45a2","keyword":"吸附","originalKeyword":"吸附"},{"id":"3a938e42-747e-4a55-9510-b0e1295b1b93","keyword":"锂","originalKeyword":"锂"},{"id":"f21a8f33-7945-45a5-b7fa-ef0b0417f9ce","keyword":"丝光沸石","originalKeyword":"丝光沸石"},{"id":"0942d5f2-15cf-4cac-9d6f-63f63ca2bcd3","keyword":"<span style=\"color:red\">ONIOM</span>","originalKeyword":"ONIOM"},{"id":"162340d0-511e-4706-aef6-2fcb41cc6821","keyword":"量子化学","originalKeyword":"量子化学"}],"language":"zh","publisherId":"cuihuaxb200410004","title":"胺类分子在LiMOR分子筛中吸附的量子化学研究","volume":"25","year":"2004"},{"abstractinfo":"应用量子力学与分子力学联合的 <span style=\"color:red\">ONIOM</span>2(B3LYP/6-31G(d,p):UFF)方法, 对 ZSM-5 分子筛中与 T6, T9 和 T12 位相邻的骨架铝的落位稳定性以及酸性强度进行了理论计算. 根据 Si/Al 替代能确定了最稳定的相邻酸性位在 Al6-Al6 位, 其次是 Al6-Al9 位, 通过 (Si/Al,H) 替代能计算确定了氢质子的落位. 计算结果证明了相邻骨架铝会导致酸性强度降低, 而且 Al6-Al9 位的酸性低于 Al6-Al6 位. 应用密度泛函理论方法进一步考察了相邻酸性位对乙烯分子吸附和质子化反应历程的影响. 结果表明, -Al-O-Si-O-Al-结构的相邻酸性位对乙烯分子的吸附以及质子化反应历程有明显影响, 尤其是使乙醇盐产物更不稳定.","authors":[{"authorName":"王善鹏","id":"c8e9ad7a-3f53-4ac8-b215-67b05e2063af","originalAuthorName":"王善鹏"},{"authorName":"王伊蕾","id":"d6b884a1-9973-4a98-acf2-ba111d776af5","originalAuthorName":"王伊蕾"},{"authorName":"曹亮","id":"562535c3-90a7-410b-a143-f3a2840c78ae","originalAuthorName":"曹亮"},{"authorName":"邢双英","id":"e49d31be-01b4-49e7-83ab-232dc12f1dbe","originalAuthorName":"邢双英"},{"authorName":"周丹红","id":"f651ea7f-5363-4c38-90dc-a9311095a866","originalAuthorName":"周丹红"}],"doi":"","fpage":"305","id":"e4b45cf8-84d3-4d9e-9899-0cab6cf0320d","issue":"4","journal":{"abbrevTitle":"CHXB","coverImgSrc":"journal/img/cover/CHXB.jpg","id":"18","issnPpub":"0253-9837","publisherId":"CHXB","title":"催化学报   "},"keywords":[{"id":"1af59a72-79c7-4365-a834-2ccc12623dde","keyword":"ZSM-5","originalKeyword":"ZSM-5"},{"id":"172b853b-2d93-4d7c-9721-f9121df8622e","keyword":"分子筛","originalKeyword":"分子筛"},{"id":"39938510-eaca-4bca-9f39-08d20a4e13b3","keyword":"相邻酸性位","originalKeyword":"相邻酸性位"},{"id":"7c116df3-b8e5-4d8f-bbb0-078ff4f433cb","keyword":"乙烯质子化","originalKeyword":"乙烯质子化"},{"id":"d7c003cb-6d6d-424a-b306-9697c0c4ea57","keyword":"<span style=\"color:red\">ONIOM</span>","originalKeyword":"ONIOM"},{"id":"40d5bb4f-868e-486b-92a5-4df7b91539b7","keyword":"方法","originalKeyword":"方法"}],"language":"zh","publisherId":"cuihuaxb200904007","title":"ZSM-5 分子筛中相邻酸性位的酸性强度及其对乙烯质子化反应影响的理论计算","volume":"30","year":"2009"},{"abstractinfo":"应用分子力学和量子力学联合的<span style=\"color:red\">ONIOM</span>2(B3LYP/6-31G(d,p):UFF)计算方法研究了H-ZSM-5分子筛上乙烯二聚反应的机理. 用40T簇模型模拟ZSM-5分子筛位于孔道交叉点的酸性位,对乙烯二聚过程的分步反应和协同反应两种机理进行了考察. 对于分步反应机理,乙烯分子首先通过π-氢键作用在酸性位形成稳定的吸附络合物,再进一步发生质子化并生成乙醇盐中间体,随后乙醇盐与第二个乙烯分子发生碳-碳键结合形成丁醇盐产物. 第一步质子化和第二步碳链聚合的活化能分别为152.88和119.45 kJ/mol, 表明乙烯质子化反应为速控步骤. 对于协同反应机理,乙烯质子化、碳-碳键和碳-氧键生成同时进行,生成丁醇盐,反应的活化能为162.30 kJ/mol, 略高于分步反应机理中的速控步骤. 计算结果表明这两种反应机理之间存在相互竞争.","authors":[{"authorName":"张佳","id":"604be8f2-cc6a-438f-a8f8-2fc752b0fcfd","originalAuthorName":"张佳"},{"authorName":"周丹红","id":"9c5220d3-fe44-4d6c-bfe3-1d6970849deb","originalAuthorName":"周丹红"},{"authorName":"倪丹","id":"e8c10975-801e-455f-a472-238bf637b3bc","originalAuthorName":"倪丹"}],"doi":"","fpage":"715","id":"1fb5a125-fd1c-4bad-bf6a-2e23911115d0","issue":"8","journal":{"abbrevTitle":"CHXB","coverImgSrc":"journal/img/cover/CHXB.jpg","id":"18","issnPpub":"0253-9837","publisherId":"CHXB","title":"催化学报   "},"keywords":[{"id":"1068ab8a-4c9d-4891-94b2-24e1f44e681a","keyword":"H-ZSM-5分子筛","originalKeyword":"H-ZSM-5分子筛"},{"id":"a02d335d-c331-4d41-9ef0-4806bbcdeb9b","keyword":"乙烯","originalKeyword":"乙烯"},{"id":"085aad99-38c6-4ae7-8d6a-9a77f4703d30","keyword":"二聚反应","originalKeyword":"二聚反应"},{"id":"59042b33-fec1-4412-9d10-3886ee96fbd0","keyword":"理论计算","originalKeyword":"理论计算"}],"language":"zh","publisherId":"cuihuaxb200808009","title":"H-ZSM-5分子筛上的乙烯二聚反应机理的理论计算研究","volume":"29","year":"2008"},{"abstractinfo":"基于76T簇模型,采用量子力学和分子力学联合的<span style=\"color:red\">ONIOM</span>2 (B3LYP/6-31G(d,p):UFF)方法研究了H-ZSM-5分子筛上环己烯芳构化反应历程.结果表明,环己烯首先吸附在分子筛酸性位上,与酸性质子共同脱除一个H2分子后,在分子筛骨架氧上生成烷氧配合物中间体；然后再脱质子得到环己二烯,同时酸性位复原；再经历脱氢和脱质子历程,最后得到产物苯,并吸附在复原的分子筛酸性位上.计算得到脱氢的活化能依次为279.64和260.21kJ/mol,脱质子的活化能依次为74.64和59.14kJ/mol.所有脱氢反应都是吸热过程,生成表面烷氧活性中间体,随后的脱质子反应能垒较低,而且是放热过程.此外,比较了环己烯在分子筛酸性位上的三个竞争反应,即脱氢、质子化和氢交换反应的活化能垒,证明环己烯优先发生脱氢反应.","authors":[{"authorName":"左士颖","id":"cd433b30-31ee-4d67-8d03-08b388111350","originalAuthorName":"左士颖"},{"authorName":"周丹红","id":"bd15c688-df45-437e-8dd8-48705f157310","originalAuthorName":"周丹红"},{"authorName":"任珏","id":"56d96c7f-aa83-45ac-9adf-60eb6ccbbcad","originalAuthorName":"任珏"},{"authorName":"王凤娇","id":"6c46d055-261a-45f5-b00a-c627ac0c2bc8","originalAuthorName":"王凤娇"}],"doi":"10.3724/SP.J.1088.2012.20346","fpage":"1367","id":"28921a49-f3c0-426d-878b-3db868660575","issue":"8","journal":{"abbrevTitle":"CHXB","coverImgSrc":"journal/img/cover/CHXB.jpg","id":"18","issnPpub":"0253-9837","publisherId":"CHXB","title":"催化学报   "},"keywords":[{"id":"6ef990cb-dbb6-4c9d-ab48-b0ea827e16ba","keyword":"H-ZSM-5分子筛","originalKeyword":"H-ZSM-5分子筛"},{"id":"56a4b20a-713b-4858-9bcc-8fa8d99e6f98","keyword":"环己烯","originalKeyword":"环己烯"},{"id":"e7864d87-8eee-4993-b67a-8a69e041b685","keyword":"芳构化","originalKeyword":"芳构化"},{"id":"27a33459-0031-43f6-a491-44bc30aa2017","keyword":"脱氢","originalKeyword":"脱氢"},{"id":"3db6efc2-0801-45a6-9e88-272c50440c81","keyword":"量子力学/分子力学","originalKeyword":"量子力学/分子力学"}],"language":"zh","publisherId":"cuihuaxb201208018","title":"H-ZSM-5分子筛上环己烯芳构化反应历程的理论研究","volume":"33","year":"2012"},{"abstractinfo":"采用<span style=\"color:red\">ONIOM</span>2(B3LYP/6-31G(d):UFF)计算方法研究了H-ZSM-5分子筛上苯与乙醇和乙烯烷基化反应历程.选取40T簇模型模拟了H-ZSM-5分子筛位于孔道交叉点的酸性位.从生成能和反应活化能角度分析并比较了苯与乙醇和乙烯烷基化反应机理.结果表明,苯与乙醇的烷基化按照分步机理进行,速控步骤的活化能为170.34 kJ/mol.而乙烯作为烷基化剂与苯反应时同时存在联合机理和分步机理,且二者之间存在一定程度的竞争,其中联合机理的活化能为167.24 kJ/mol,分步机理速控步骤的活化能为155.20 kJ/mol.比较苯与乙醇和乙烯发生烷基化反应的机理可以看出,二者作为烷基化试剂对烷基化反应性能影响不大.","authors":[{"authorName":"聂小娃","id":"b4088d96-194b-4d0a-9351-b43178b30288","originalAuthorName":"聂小娃"},{"authorName":"刘新","id":"2e953a52-3242-4bb4-bea5-0f7b6a6b820b","originalAuthorName":"刘新"},{"authorName":"宋春山","id":"4e8c92a4-aa48-4753-93ef-31a6d87ae015","originalAuthorName":"宋春山"},{"authorName":"郭新闻","id":"2ea21828-99bf-418d-b88e-ca2b3aaf1564","originalAuthorName":"郭新闻"}],"doi":"","fpage":"453","id":"51c0bf9b-9e1d-410e-9ded-41626daf7d9f","issue":"5","journal":{"abbrevTitle":"CHXB","coverImgSrc":"journal/img/cover/CHXB.jpg","id":"18","issnPpub":"0253-9837","publisherId":"CHXB","title":"催化学报   "},"keywords":[{"id":"b08094ac-bd2e-4072-a3ad-b2320809ba56","keyword":"苯","originalKeyword":"苯"},{"id":"aaf6cf5b-50ff-40a7-a64f-8084a8cdcfb3","keyword":"乙醇","originalKeyword":"乙醇"},{"id":"e65df130-b197-49fd-9fe0-b347fa5ada83","keyword":"乙烯","originalKeyword":"乙烯"},{"id":"56111fb5-f731-4340-8083-53fd4b5fc9d1","keyword":"烷基化反应","originalKeyword":"烷基化反应"},{"id":"bc75bf95-0251-4823-b793-c3b9b5f6a9ec","keyword":"反应机理","originalKeyword":"反应机理"},{"id":"0a2d36dd-45e8-43d3-9a7f-af2187683110","keyword":"H-ZSM-5","originalKeyword":"H-ZSM-5"},{"id":"ee51fa57-3c15-4a57-aae0-7a464c4fb583","keyword":"理论计算","originalKeyword":"理论计算"}],"language":"zh","publisherId":"cuihuaxb200905015","title":"H-ZSM-5分子筛上苯与乙醇和乙烯烷基化反应的理论研究","volume":"30","year":"2009"},{"abstractinfo":"用24T模型和两种<span style=\"color:red\">ONIOM</span>2方法(QM/QM和QM/MM)研究了杂原子H-AlMOR和H-BMOR分子筛的结构、酸性及其对吡啶的吸附性能. 吸附热以及分子筛的几何结构和电子结构数据表明, H-BMOR的B酸性远远弱于H-AlMOR, 因此二者可分别应用于对酸性要求不同的催化反应. 采用QM/QM计算得到的吡啶在H-AlMOR上的吸附热(219.3 kJ/mol)与实验结果(200 kJ/mol)比较接近. QM/QM方法尽管耗时较多,但能得到更精确的结果,而QM/MM方法可用于定性研究及对模型结构的初步预测. 吸附复合物的结构参数及红外振动频率等数据表明,吡啶在两种分子筛上吸附时均发生了质子转移,生成PyH+…ZeO-离子对. 此外,吸附复合物中还存在多重氢键作用.","authors":[{"authorName":"袁淑萍","id":"4251a81d-efe6-4d9c-a958-a860c8b4e8b5","originalAuthorName":"袁淑萍"},{"authorName":"段云波","id":"de48b073-da2c-4e6d-b592-0a3f363eab99","originalAuthorName":"段云波"},{"authorName":"王建国","id":"4e42a1f0-87d6-416d-bd74-45bc152999fa","originalAuthorName":"王建国"},{"authorName":"李永旺","id":"c65496c8-448f-4385-8634-d64761a0694c","originalAuthorName":"李永旺"},{"authorName":"焦海军","id":"72b47c74-d3b9-4ad0-ba0e-9926b6b21de7","originalAuthorName":"焦海军"}],"doi":"","fpage":"664","id":"694070f2-26c1-4952-be36-e08f93c85fa9","issue":"8","journal":{"abbrevTitle":"CHXB","coverImgSrc":"journal/img/cover/CHXB.jpg","id":"18","issnPpub":"0253-9837","publisherId":"CHXB","title":"催化学报   "},"keywords":[{"id":"284f68b6-78e2-40f6-bbcc-a700694c0e31","keyword":"丝光沸石","originalKeyword":"丝光沸石"},{"id":"96c6478b-b5c3-4b9e-8fd5-c541fe60ceff","keyword":"吡啶","originalKeyword":"吡啶"},{"id":"128d38ef-f5f3-4e63-8d12-33fe0679b274","keyword":"吸附","originalKeyword":"吸附"},{"id":"429ac92d-45e2-49ab-8ae9-2fa8eb277d29","keyword":"<span style=\"color:red\">ONIOM</span>方法","originalKeyword":"ONIOM方法"},{"id":"006aadf2-e4af-4311-9838-8a7522994d9c","keyword":"量子化学","originalKeyword":"量子化学"}],"language":"zh","publisherId":"cuihuaxb200608006","title":"吡啶在H-MOR分子筛孔道中吸附的量子化学研究","volume":"27","year":"2006"},{"abstractinfo":"应用密度泛函理论和量子力学与分子力学联合的<span style=\"color:red\">ONIOM</span>2方法对含Ti的MFI分子筛(TS-1)中Ti4+离子在三种不同骨架落位上所表现的Lewis酸性进行了理论研究. 利用碱性探针分子(CO, NH3, 乙腈和吡啶)在骨架Ti活性中心的吸附作用,对吸附络合物的几何结构和吸附能进行了计算,并通过自然键轨道(NBO)分析考察了吸附络合物的电子结构. 结果表明,骨架Ti在T12位表现出明显的Lewis酸性,对NH3分子有较强的吸附作用. NBO分析表明,骨架Ti活性中心的Lewis酸性是由于 Ti - O 键的空σ反键轨道接受碱性探针分子提供的孤对电子;NH3分子吸附导致Ti4+离子由近正四面体中心对称变为五配位的三角双锥对称.","authors":[{"authorName":"王伊蕾","id":"1f073170-68c6-41f7-8df2-e65ed4adce46","originalAuthorName":"王伊蕾"},{"authorName":"邢双英","id":"ebbadb9a-45f3-4e3c-8b2b-b045acf7636a","originalAuthorName":"邢双英"},{"authorName":"曹亮","id":"b7f8730a-460d-4062-87d3-2c14929a502a","originalAuthorName":"曹亮"},{"authorName":"王善鹏","id":"f7416697-a61c-435c-a2af-26842cfabb69","originalAuthorName":"王善鹏"},{"authorName":"周丹红","id":"8b1ada31-b66b-4837-8f6c-56d32e912e78","originalAuthorName":"周丹红"}],"doi":"","fpage":"24","id":"db68579a-3685-43e2-b567-a26067f45e15","issue":"1","journal":{"abbrevTitle":"CHXB","coverImgSrc":"journal/img/cover/CHXB.jpg","id":"18","issnPpub":"0253-9837","publisherId":"CHXB","title":"催化学报   "},"keywords":[{"id":"e35960e1-df4b-419e-982c-0e6d3cf7c576","keyword":"钛硅分子筛","originalKeyword":"钛硅分子筛"},{"id":"16ffd23e-8dc5-4f9a-8d90-13254e88294b","keyword":"Lewis酸性","originalKeyword":"Lewis酸性"},{"id":"4ff08deb-7631-4e9b-8463-29e73a06509b","keyword":"吸附","originalKeyword":"吸附"},{"id":"fb83ba40-cccc-4355-b0f7-f5cb0da615a9","keyword":"密度泛函理论","originalKeyword":"密度泛函理论"},{"id":"7173b023-af2a-4565-a711-798adbcd6806","keyword":"自然键轨道分析","originalKeyword":"自然键轨道分析"}],"language":"zh","publisherId":"cuihuaxb200901007","title":"TS-1分子筛Lewis酸性的理论研究","volume":"30","year":"2009"},{"abstractinfo":"应用<span style=\"color:red\">ONIOM</span>计算方法研究了MCM-22分子筛超笼12元环上存在两个酸性位时的酸强度及其与骨架铝之间距离的关系,并研究了乙烯和苯分子吸附的规律.计算采用52T簇模型和B3LYP/6-31G* */MNDO方法.结果表明,存在两个酸性位且两个骨架铝之间间隔1个骨架硅时,酸强度比孤立的酸性位明显降低;当间隔的硅原子数增加时,酸强度呈上升趋势,间隔3个以上骨架硅时,其酸强度与孤立的酸性位几乎没有差别.对于乙烯的吸附,当两个骨架铝之间间隔1～4个骨架硅时,其吸附能几乎没有差别(31～35 kJ/mol);对于苯的吸附,当两个骨架铝之间间隔1个骨架硅时,其吸附能有所提高,因为两个桥羟基同时对苯分子产生氢键吸附作用.当两个骨架铝之间的距离增大时,苯的吸附能几乎相同(21～29 kJ/mol).若两个乙烯分子或苯分子同时吸附在双酸性位上,其吸附能与单个分子在孤立酸性位吸附时几乎没有差别.应用自然键轨道计算分析了吸附配合物的电子结构,进一步探明了乙烯和苯在分子筛酸性位上吸附的本质.","authors":[{"authorName":"倪丹","id":"4bd2d2ab-9d3e-42b7-a319-40fef777b46a","originalAuthorName":"倪丹"},{"authorName":"周丹红","id":"c1ac70b9-1cfd-440e-8848-512dcb62f28c","originalAuthorName":"周丹红"},{"authorName":"张佳","id":"e68dc7b3-7132-4145-a2d4-6c039394d2b5","originalAuthorName":"张佳"}],"doi":"","fpage":"366","id":"83ef7b9f-48ba-4676-9826-9a6456d51b32","issue":"4","journal":{"abbrevTitle":"CHXB","coverImgSrc":"journal/img/cover/CHXB.jpg","id":"18","issnPpub":"0253-9837","publisherId":"CHXB","title":"催化学报   "},"keywords":[{"id":"454c6fb6-f076-40ac-8b72-469faa5aabee","keyword":"密度泛函","originalKeyword":"密度泛函"},{"id":"4c331115-91b3-4283-af4a-8d8b9523f4b6","keyword":"MCM-22分子筛","originalKeyword":"MCM-22分子筛"},{"id":"a6d4034d-e4da-4254-b4d7-a7a961e6c85f","keyword":"乙烯","originalKeyword":"乙烯"},{"id":"08f90f1b-0cca-4458-be40-02b4f87f11e9","keyword":"苯","originalKeyword":"苯"},{"id":"9ea912f2-f80f-4812-9382-ee68c76bd0de","keyword":"吸附能","originalKeyword":"吸附能"}],"language":"zh","publisherId":"cuihuaxb200804012","title":"应用理论计算研究MCM-22分子筛相邻酸性位上乙烯和苯的吸附","volume":"29","year":"2008"},{"abstractinfo":"应用量子力学和分子力学联合的<span style=\"color:red\">ONIOM</span>2(B3LYP/6-31G(d,p):UFF)方法,采用包含分子筛孔道结构的78T簇模型,对HZSM-5分子筛上乙烯芳构化过程中C4至C6中间体的反应历程进行了研究,探讨了分子筛的酸催化机理和择形催化作用.结果表明,作为乙烯二聚产物的表面正丁基烷氧络合物(C4)直接与乙烯作用得到正己基烷氧络合物(C6),在分子筛孔穴尺寸的限制下,很难实现碳链的折叠环化.按照间歇反应历程,丁基烷氧络合物先发生C-O键断裂,脱质子生成1-丁烯,然后在酸性位上再与乙烯加成,在分子筛表面生成3-甲基戊基烷氧络合物,该烷氧络合物脱除质子给分子筛,同时环化生成甲基环戊烷,后者再与分子筛酸性质子共同脱除氢分子,生成不稳定的碳正离子中间体,然后重构成环己烷正离子.丁基烷氧络合物脱质子的活化能为158.42kJ/mol;1-丁烯与乙烯加成反应的活化能为130.71 kJ/mol;3-甲基戊基烷氧络合物脱氢环化生成甲基环戊烷的活化能为122.06kJ/mol,由于孔穴的限域作用,五员环的甲基环戊烷是重要的中间体.","authors":[{"authorName":"曹亮","id":"0e5100ac-32b1-4019-bd89-3f9c9df69be1","originalAuthorName":"曹亮"},{"authorName":"周丹红","id":"6f730860-6730-42de-a197-2a98acbb8300","originalAuthorName":"周丹红"},{"authorName":"邢双英","id":"03212ae5-c7fb-4f24-89fc-59cb167dc104","originalAuthorName":"邢双英"},{"authorName":"李新","id":"fc1a25d9-3537-4763-a0cd-d61b1861e402","originalAuthorName":"李新"}],"doi":"10.3724/SP.J.1088.2010.91121","fpage":"645","id":"9bedf05f-224e-47ab-8b8d-5c1a080f9953","issue":"6","journal":{"abbrevTitle":"CHXB","coverImgSrc":"journal/img/cover/CHXB.jpg","id":"18","issnPpub":"0253-9837","publisherId":"CHXB","title":"催化学报   "},"keywords":[{"id":"5315314c-e2f8-4d88-8eb9-14113a2cc3f3","keyword":"密度泛函理论","originalKeyword":"密度泛函理论"},{"id":"8397c255-55b4-402e-849a-4c34f6faedb2","keyword":"乙烯","originalKeyword":"乙烯"},{"id":"c5ef8e6b-f778-4300-b765-bdc565f1cb3b","keyword":"芳构化","originalKeyword":"芳构化"},{"id":"9e2ee640-54e5-4f09-a018-24da88b300fe","keyword":"HZSM-5分子筛","originalKeyword":"HZSM-5分子筛"},{"id":"e5ea5fbe-7631-4d1f-bec6-54146098a187","keyword":"反应机理","originalKeyword":"反应机理"},{"id":"16874a35-eae0-4f5e-b7c0-7da249fc6d95","keyword":"禁闭效应","originalKeyword":"禁闭效应"}],"language":"zh","publisherId":"cuihuaxb201006008","title":"HZSM-5分子筛上乙烯芳构化过程中C4至C6中间体的反应机理","volume":"31","year":"2010"}],"totalpage":2,"totalrecord":12}