Studies on the Effects of Supports and Metal Nanoparticle Sizes of Supported Catalysts for Asymmetric Hydrogenation of Aromatic Ketones and Hydrogenolysis of Sorbitol

潜手性底物的不对称加氢反应是获得高纯度手性化合物的重要手段之一。以芳香酮不对称加氢反应为例，Noyori等开发的[(R)-BINAP-Ru-(1R，2R)-DPEN]Cl2均相催化剂具有很高的催化活性和产物对映选择性，但是均相体系产物分离和催化剂循环使用困难，而均相催化剂的多相化是解决该矛盾的有效途径之一。 山梨醇是生物质开发过程12个重要平台分子之一，工业上可以通过葡萄糖加氢反应大量生产。其氢解产物乙二醇和丙二醇都是重要的化工原料，传统的生产工艺为烯烃先环氧化再水合的方法。生物质途径制备二元醇是石油化工途径的替代方法之一。目前，工业上应用的氢解催化剂多为贵金属催化剂，因此研发廉价、高效、可...Asymmetric hydrogenation of prochiral substrates is one of the effective methods to obtain high enantioselective compounds. The [(R)-BINAP-Ru-(1R,2R)-DPEN]Cl2 catalyst developed by Noyori was demonstrated as one of the effective homogeneous catalysts for the asymmetric hydrogenation of aromatic ketones. It exhibited not only excellent activity but also high ee value. However, the separation and re...学位：理学博士院系专业：化学化工学院化学系_物理化学(含化学物理)学号：1912005140308

中国における高等教育の変貌と動向 : 2005年以降の動きを中心に

はしがき　黄福涛...i 第1章　世界一流大学の構築 : 政策・効果・課題　黄福涛...1 第2章　大学の多様化と機能分化 : 3大学の調査を例に　李敏...13 第3章　「中外合作弁学」の新たな展開　叶林...23 第4章　民営高等教育と「独立学院」の新たな展開　鮑威・沈鴻敏...33 第5章　大学入試改革　謝妍笑...45 第6章　大学カリキュラム改革 : 「通識教育」カリキュラム改革を中心に　史媛媛...53 第7章　拡張路線にある中国の大学院教育の展開　李敏...69 第8章　中国における大学教授職の国際的な活動およびその規定要因に関する実証研究　呉嫻...87 第9章　中国における高等教育の質保証 : 「本科教学工作評価」を中心に　林師敏...10

Selective Oxidation of Methane to Methanol in Oleum over Pd/C Catalyst

以PdCl2为前驱体,采用浸渍法制备了Pd/C催化剂,并在发烟硫酸中考察了其催化甲烷选择氧化反应的性能,采用X射线粉末衍射、X射线光电子能谱、高分辨透射电镜和CO吸附等方法对催化剂进行了表征.甲烷选择氧化反应得到的主产物硫酸单甲酯经水解后得到甲醇,在5%Pd/C催化剂、Pd用量30μmol、反应温度180℃、反应压力4.0 MPa、反应时间4 h和发烟硫酸中SO3含量为50%的优化工艺条件下,甲烷转化率为23.6%,甲醇的选择性和收率分别为69.5%和16.4%,在一定程度上可实现催化剂的多次重复使用.Pd/C催化剂上的甲烷选择氧化反应可能遵循亲电取代机理,催化性能与Pd负载量、Pd粒子尺寸和分散度等有关.The selective oxidation of methane to methanol over Pd/C catalysts generated from a PdCl2 precursor was investigated in oleum.Characterization of the catalysts was performed by X-ray diffraction,X-ray photoelectron spectroscopy,high-resolution transmission electron microscopy,and CO adsorption.The major product in the oxidation reaction was methyl bisulfate,which was then hydrolyzed into methanol.Methane conversion of 23.6% with methanol selectivity of 69.5% and yield of 16.4% was achieved under the optimum conditions of 5%Pd/C,30 μmol Pd,reaction temperature 180 ℃,methane pressure 4.0 MPa,reaction time 4 h,and 50% sulfur trioxide concentration.After facile separation with the reactants and pretreatment,the catalyst could be reused several times with considerable stability.The selective oxidation of methane catalyzed by Pd/C catalysts in oleum possibly involved an electrophilic substitute mechanism.The catalytic performance was related to the Pd loading,dispersion,and particle size.国家自然科学基金(20473065);; 福建省科技重大专项(2005HZ01-3

C–X(X = Cl, Br, I) bond dissociation energy as a descriptor for the redispersion of sintered Au/AC catalysts

负载型Au基催化剂在工业过程中具有非常广泛的潜在应用,如催化加氢/脱氢过程、精细化学品合成、能源催化转化及环境保护等过程,表现出很高的催化活性和选择性.Au基催化剂活性物种或活性中心基本由纳米粒子或化合物构成,但在应用过程中因Ostwald熟化效应或粒子迁移作用,尤其是高温高压等苛刻反应条件下,均随应用时间延长从小尺寸粒子逐渐长为大粒子,造成活性降低或完全失活,这也是负载型催化剂失活的最主要原因之一.其中因成本、稀缺等特性,负载型Au催化剂的烧结问题是影响和制约其应用的主要因素.除可通过载体改性、助剂和官能团配位稳定等方法来延缓其失活过程外,对已烧结催化剂的高效、快捷和绿色的再分散/再生过程也具有基础和应用研究的重要意义.活性炭载Au催化剂(Au/AC)广泛应用于乙炔氢氯化反应中,以期替代高毒性的汞基催化剂,但在反应过程中因高活性的Au~(3+)物种易被还原而形成Au~0物种进而烧结导致失活;如新鲜Au/AC催化剂表面的Au粒子尺寸为1-2 nm,经乙炔氢氯化反应后变为33 nm左右;随之在453 K、0.1 MPa、乙炔体积空速(GHSV)为600 h~(-1)、氯化氢与乙炔摩尔比为1.1的反应条件下,乙炔转化率从81.8%降至11.2%.如何有效对大粒子Au再分散/再生可为其应用提供有力支撑.有研究表明,气相CHI_3在甲醇羰基化反应过程中明显改变Au/AC表面的Au粒子尺寸;或采用浓盐酸或王水也可将烧结的Au/AC催化剂进行再分散/再生.但已有的Au基催化剂再分散/再生过程均伴随着强酸、强氧化或高毒性在分散剂的应用,对环境的影响及后续处理有明显的局限性,且再分散机理尚不明确.在前期工作基础上,本文采用系列卤代烃(碘代烃、溴代烃和氯代烃)对烧结的Au/AC进行再分散/再生研究.结果表明,在室温常压条件下CHI_3可以快捷高效地对烧结Au/AC催化剂进行再分散/再生,具有最优的再分散性能;通过对系列碘代烃C-I键的解离能分析,发现C-I解离能越低越有利于大粒子Au的再分散.同时,溴代烃和氯代烃对烧结的Au/AC催化剂也具有再分散能力,但比碘代烃的再分散效率低.C-X键的解离能与再分散效率有高相关性,即C-X键的解离能越低越有利于Au的再分散.总体上,三类卤代烃再分散效率高低顺序为C-I>C-Br>C-Cl.进而,通过不同分散过程中Au粒子分散状态推测了卤代烃对Au粒子的再分散机理,即卤代烃先在Au粒子表面化学吸附,然后C-X键解离,形成Au-X物种,小粒子Au在AC表面聚集并稳定,最后形成高分散Au粒子(粒径<1 nm)催化剂.以乙炔氢氯化反应考察了再生Au/AC催化剂性能,结果表明,该催化剂上乙炔转化率可达79.4%,基本恢复至初始水平,且该方法可对失活催化剂进行多次高效再生.Disintegration or redispersion of supported sintered gold nanoparticles(Au NPs) in the presence of alkyl halide can give catalyst regeneration or redispersion of sintered Au catalysts. The selectivity of alkyl halides, temperature and size distributions were investigated to elucidate the redispersion of Au NPs during halide-induced decomposition. This study proved that the alkyl halide induced the redispersion of sintered Au NPs which depended on the R–X(X = I, Br, Cl) bond dissociation energy(BDE) and thus provided a simple descriptor for the regeneration of inactive supported Au cata-lysts. A correlation between the BDE of R–X and dispersion efficiency was established. The tendency for disintegration and redispersion followed the R–X BDE of the alkyl halide. Compared to alkyl chlorides and bromides, iodides were more efficient for redispersing sintered Au NPs. As a descriptor, the BDE of R–I played a crucial role in particle redispersion. These findings provided insights into the mechanism of organic halide-induced Au NP disintegration and the effect of the halide type on the redispersion of sintered catalysts.国家自然科学基金(21403178,21473145,21503173,91545115);; 教育部创新团队发展计划(IRT_14R31);; 福建省青年教师教学科研基金(JA15003

Selective oxidation of methane to methanol in oleum over Pd/C catalyst

The selective oxidation of methane to methanol over Pd/C catalysts generated from a PdCl2, precursor was investigated in oleum. Characterization of the catalysts was performed by X-ray diffraction, X-ray photo-electron spectroscopy, high-resolution transmission electron microscopy, and CO adsorption. The major product ill the oxidation reaction was methyl bisulfate, which was then hydrolyzed into methanol. Methane conversion of 23.6% with methanol selectivity of 69.5% and yield of 16.4% was achieved under the optimum conditions of 5% Pd/C, 30 mu mol Pd, reatction temperature 180 degrees C, methane pressure 4. 0 MPa, reaction time 4 h, and 50% sulfur trioxide concentration. After facile separation with the reactants and pretreatment, the catalyst could be reused several times with considerable stability. The selective oxidation of methane catalyzed by Pd/C catalysts in oleum possibly involved an electrophilic substitute mechanism. The catalystic performance was related to the Pd loading, dispersion, and particle size

Selective methylation of toluene using CO2 and H2 to para-xylene

二甲苯（PX）是石化工业的基本有机化工原料之一，主要用于生产三大合成材料—合成树脂、合成纤维和合成橡胶。随着我国下游产业的快速发展，PX的需求量迅猛增长，进口依存度大于50%。袁友珠教授课题组提出使用CO2和H2替代甲醇作为甲苯烷基化试剂，利用CO2和H2在相对较低温度下生成的甲氧基中间体（无需经甲醇）直接与甲苯烷基化。化学化工学院2018级博士生左佳昌为论文第一作者，博士生陈伟坤、硕士生刘佳以及醇醚酯化工清洁生产国家工程实验室（厦门大学）段新平博士和叶林敏博士等参与了论文的部分研究。该研究结果已分别申请了中国发明专利（申请号201911149539.2, 2019）和国际专利（申请号PCT/CN2020/077412, 2020）。【Abstract】Toluene methylation with methanol to produce xylene has been widely investigated. A simultaneous side reaction of methanol-to-olefin over zeolites is hard to avoid, resulting in an unsatisfactory methylation efficiency. Here, CO2 and H2 replace methanol in toluene methylation over a class of ZnZrOx–ZSM-5 (ZZO-Z5) dual-functional catalysts. Results demonstrate that the reactive methylation species (H3CO*; * represents a surface species) are generated more easily by CO2 hydrogenation than by methanol dehydrogenation. Catalytic performance tests on a fixed-bed reactor show that 92.4% xylene selectivity in CO-free products and 70.8% para-xylene selectivity in xylene are obtained on each optimized catalyst. Isotope effects of H2/D2 and CO2/13CO2 indicate that xylene product is substantially generated from toluene methylation rather than disproportionation. A mechanism involving generation of reactive methylation species on ZZO by CO2 hydrogenation and migration of the methylation species to Z5 pore for the toluene methylation to form xylene is proposed.This work was supported by the National Key Research and Development Program of China (2017YFA0206801), the National Natural Science Foundation of China (21972113), and the Program for Innovative Research Team in Chinese Universities (IRT_14R31).该工作得到了国家重点研发计划（2017YFA0206801）、国家自然科学基金（21972113、91545115）和教育部创新团队（IRT_14R31）的资助

原生态文化与中国传统

第九届人类学高级论坛于2010年6月23～25日在贵州省凯里学院举行。会议期间,《光明日报》国学版主编梁枢先生组织了一个关于"原生态文化与中国传统"的小型座谈会,会议由广西民族大学徐杰舜教授主持,参加人员有中国人民大学郑杭生教授、中国社会科学院叶舒宪研究员、四川大学徐新建教授、厦门大学彭兆荣教授、中国人民大学陆益龙副教授、浙江师范大学林敏霞博士等。座谈会就原生态文化与中国传统文化尤其是国学的关系展开了深入探讨

Advances in Catalysts for Selective Hydrogenation of Dimethyl Oxalate

简单介绍了草酸二甲酯加氢制乙二醇是“煤制乙二醇“技术路线中的一个关键步骤,通过调控催化剂活性,草酸二甲酯经选择性加氢还可得到乙醇酸甲酯和乙醇;概述了国内外草酸二甲酯选择性加氢分别制乙醇酸甲酯、乙二醇和乙醇反应催化剂的最新研究进展;重点探讨了通过改变催化剂组成、促进剂以及反应条件,进而实现草酸二甲酯加氢反应活性和产物选择性调控的研究结果;指出了草酸二甲酯选择性加氢催化剂研发过程中存在的问题和挑战以及未来的发展趋势。It is introduced that the hydrogenation of dimethyl oxalate(DMO) to ethylene glycolate(EG) is a key step for "syngas to EG" process.Methyl glycolate(MG) or ethanol can also be produced via the selective hydrogenation of DMO over well-designed catalysts with proper activity.The latest progresses in the catalyst research for the hydrogenations of DMO to MG,EG and ethanol are reviewed.The achievements in controlling the reaction activity and product selectivity in the hydrogenation of DMO by adjusting the catalyst composition,additives and the reaction conditions are investigated.In addition,questions in the present research and trends in the future research for the catalysts of the selective hydrogenation are discussed.科技部“973”课题(2011CBA00508); 国家自然科学基金项目(21173175和21303141); 高等学校博士学科点优先发展领域课题(20110121130002); 教育部长江学者和创新团队发展计划(IRT1036

THE PATHOGENICITY OF GNATHOSTOMA HISPIDUM TO SWINE

猪颚口线虫病的临床症状是病猪经常呕吐、食欲减退、消瘦和体重减轻 ,早期血检嗜酸性细胞增高。本病的主要致病器官是胃和肝脏。胃的主要病变是胃底布满虫洞、粘膜增厚、发炎和溃疡。肝的病变是结缔组织增生、虫道出血、肝细胞索紊乱、肝细胞脂肪变性、萎缩和坏死。文中讨论了幼虫在体内的移行途径和本病的防治问题。The typical symptom of Gnathostomiasis is that the infected swine keep vomiting,anorexia,emaciated,lose weight and its eosinophil leukocyte increased.Swine stomach and liver are the main organ damaged.The main pathological changes is that the bottom of stomach is punctured by the parasite,its mucosa become thicker,inflamed and ulcer.The connected tissue of liver proliferated.The pathway along which the parasite migrate become hemorrhage,with the liver cell cord disordered.The liver cell fatty degenerated,withered and become necrosis.The way of the larve of Gnathostoma hispidum migrating in the body of swine and the control of Gnathostomiasis are discussed in this paper

闽南地区5869例儿童社区获得性肺炎患者病原学特点分析

目的通过对闽南地区社区获得性肺炎(CAP)患儿病原特点进行分析,为CAP早期预警、预防和早期经验治疗提供指导和依据。方法收集我院2015年1月至2017年5月5 869例CAP患儿静脉血、呼吸道分泌物及痰标本分别进行肺炎支原体(MP)、呼吸道病毒检测以及细菌培养和鉴定。结果 5 869例CAP患儿中明确病原体感染4 931例,其中单纯细菌感染3 054例,单纯病毒感染966例,单纯MP感染620例,混合感染291例,未检出病原体938例。细菌性病原主要以肺炎链球菌、流感嗜血杆菌和卡他莫拉菌为主,在各季节检出率不同且男性多于女性,主要在低龄儿童中检出。病毒感染者主要分布于低龄儿童,夏季检出率最高,病原以呼吸道合胞病毒(RSV)为主,占68.22%。该类患者在性别上比较差异无统计学意义。MP感染者中女性多于男性,主要分布于大龄儿童,冬季检出率最高。结论本地区CAP患儿病原检出率由高到低分别为细菌、病毒和MP。细菌和MP检出率在患儿中具有性别差异,各种病原在不同年龄段儿童及季节中检出率不同。厦门市第二批青年创新创业人才项目(2015-A-03