A study on hydrogenolysis of C-O chemical bonds in esters over supported nanocatalysts with coinage metals

大宗有机含氧化工原料的生产是当前碳一化工的一大重点领域，这就涉及到如何将碳与氧有机利用。酯类化合物有广泛的来源和相对低廉的价格，酯的碳氧键氢解可以得到具有高价值的醇类化工产品，在大宗有机含氧化工原料的合成中扮演着重要的角色。通过对酯类化合物氢解制醇的研究具有重要的科学研究和化工应用价值。乙醇酸甲酯和乙二醇是重要的有机合成中间体，在化工生产，医药产品等领域有广泛的应用。“煤制乙二醇”更是近年来中国大力发展的工业项目，包括神华集团在内的各大型企业陆续启动“煤制乙二醇”项目。作为“煤制乙二醇”中重要的一环，草酸酯加氢制乙二醇是“煤制乙二醇”技术路线中最重要的核心和关键步骤，无论基础研...At present, one of the major project among the C1 chemical research is to produce bulk commodities of organic oxygen-contained chemicals, which needs to utilize the carbon and oxygen together. The hydrogenolysis of CO bond in ester to alcohol is one of the proposal approaches, in which ester has wide source and is cheap. Therefore, research on the hydrogenolysis of CO bonds in este...学位：理学博士院系专业：化学化工学院_物理化学学号：2052013015388

非单调混沌神经元的电路实现

提出了一种非单调Ｈｏｐｆｉｅｌｄ型混沌神经元的电路设计，在电路中我们把轨迹状态参数的调节用可调电阻来实现，通过改变可调电阻的阻值就可以改变神经元的吸引子性质，从而可以很方便地通过实验来研究混沌神经元的动力学行为。应用该电路，我们成功地观测到了神经元的不动点、倍周期分岔和混沌现象

Hopfield神经网络的存贮容量

我们把理论推导与数值模拟相结合，得出了一个较好的误差函数近似解析式。应用该解析式分析了Ｈｏｐｆｉｅｌｄ神经网络的绝对存贮容量，得到了一更严格的结果

An Investigation of the Professional Development of Primary and Secondary School P. E. Backbone Teachers in Fujian Province

采用文献法、调查法、统计法、逻辑法等研究方法,以参加2013—2015年福建省基础教育万名骨干教师培训中的190名中小学体育骨干教师为调查对象,对教师基本情况和教师专业发展的认识、态度、知识、能力、继续教育等现状进行调查,在此基础上对教师专业发展现状进行分析,总结出我省中小学体育骨干教师专业发展的特点及存在的问题,并提出相应的建议,给我省中小学体育教师培训机构的改革提供依据,同时为我省中小学体育教师专业发展提供参考与借鉴,为进一步深化我省中小学体育教育改革提供人才保障.结果表明:1)目前,福建省中小学体育骨干教师以年富力强者居多,年龄、职称结构较合理;教师专业发展意识强,学历层次由大专逐步向本科、硕士过度,但硕士比例小;2)教师专业发展态度端正,职业的稳定性和责任感强烈,但部分年轻教师缺乏专业发展的自主性;3)教师对专业知识的掌握比较扎实,主要通过互联网、图书资料、专家报告或讲座等方法来获取专业知识;4)专业能力水平方面,教师在体育教学、课外指导、体育保健、现代教育技术运用等方面能力比较强,而创新教育和科研两方面能力相对比较薄弱;5)当下,我省中小学体育骨干教师最需要强化的培训是课题申报技能、论文写作能力、专题讲座能力、教育科研方法、提高学历层次、教学设计能力,其中提高科研能力和水平是教师们最迫切的愿望.2014年福建省中青年教师教育科研项目(社科A类)(JAS14023

应用信噪比理论分析三维转动角神经网络模型的存储容量

人工神经网络是最近发展起来的十分热门的交叉学科,它涉及到生物、电子、计算机、数学和物理等学科,有着非常广泛的应用前景.本文讨论的是一类多值神经网络模型一一Q态三维转动角神经网络模型的存储容量 该模型是Hopfield神经网络模型、四态复数神经网络模型、复相角神经网络模型和多态四元数神经网络模型的推广,具有一定的理论研究价值;可以在灰度或彩色图像识别中得到应用

应用信噪比理论分析复相角神经网络的存储容量

本文应用信噪比理论分析了复相角神经网络模型的存储容量。分析和研究结果表明，当神经元转动态的数目很小时，模型的存储容量与Ｈｏｐｆｉｅｌｄ神经网络模型的存储容量相同；当神经元转动态的数目很大时，存储容量与神经元转动态数目的平方成反比

基于分子技术的1株产毒藻藻际细菌多样性分析

采用构建16SrDNA克隆文库的方法,对实验室保存的1株产毒塔玛亚历山大藻在不同时期的藻际细菌群落多样性进行了分析.限制性片段长度多态性(restrictionfragment length polymorphism,RFLP)结果表明,塔玛亚历山大藻藻际微生物的16SrDNA克隆文库中的克隆子总共可分为34种基因型,选取各谱型的代表克隆子测定其16SrDNA片段核苷酸序列,将所获得的序列与GenBank数据库进行BLAST比对,结果表明所有基因型分属于2个细菌类群:变形细菌门(Proteobacteria)和拟杆菌门(Bacteroidetes).在延滞期的藻培养液中,α-Proteobacteria占36.4%,β-Proteobacteria占9.1%,γ-Proteobacteria占27.3%,拟杆菌门(Bacteroidetes)占27.3%;在指数后期的培养液中,α-Proteobacteria占53.3%,β-Proteobacteria占13.3%,γ-Proteobacteria占6.7%,拟杆菌门(Bacteroidetes)占26.7%;在稳定期的培养液中,α-Proteobacteria占47.8%,β-Proteobacteria占8.7%,γ-Proteobacteria占21.7%,δ-Proteobacteria占4.3%,拟杆菌门(Bacteroidetes)占17.4%;其中有不少克隆子与已知序列同源性低于94%,表明塔玛亚历山大藻藻际环境中附着有新的未开发的微生物资源,这些细菌可能在微藻的生消过程中起着重要的调控作用,所以本研究结果在赤潮微生物调控中具有重要的理论意义和应用价值

Biological nitrogen fixation in the upper water column in the south Taiwan Strait during summer 2011

2011年6—7月,利用15n2示踪法实测了台湾海峡南部海域的生物固氮速率,结合温度、盐度、天然颗粒物氮同位素组成的分布,分析并讨论了影响研究海域生物固氮速率的环境因素。结果表明,夏季台湾海峡南部海域的生物固氮速率介于168—1080 nMOl M-3d-1之间,平均为537 nMOl M-3d-1,较高的生物固氮速率大多出现在次表层水体中。研究站位的积分固氮速率变化范围为11—40μMOl M-2d-1,平均为23μMOl M-2d-1。积分固氮速率的空间变化与不同水团的影响有关,在受黑潮水影响的海域,生物固氮速率较高,而在上升流和受河流冲淡水影响的海域,生物固氮速率较低,说明较低的水温及较高的无机氮营养盐可能会抑制研究海域的生物固氮作用。研究海域天然颗粒物δ15n与生物固氮速率之间呈现良好的负相关关系,表明天然颗粒物氮同位素组成可定性指征研究海域生物固氮作用的强弱。Biological N2fixation in marine environments is a major component in the ocean nitrogen budget and plays an important role in global carbon cycles through the sequestration of atmospheric carbon dioxide and production of marine organic matter.N2fixation could be regulated by the abundance and chemical speciation of nutrients and many trace elements in seawater.Recent studies have revealed that N2fixation is much more widespread in marine environments than previously thought.However,little is known about the N2fixation in the Taiwan Strait,especially on N2fixation rates,and their relationship with environmental parameters.The major objectives of this study were to determine the N2fixation rates and their spatial distributions and to explore major physicochemical controlling factors in the south Taiwan Strait.During June and July 2011,seawater samples were collected from ten stations at two transects in the south Taiwan Strait for the measurements of N2fixation rate using the15N2tracer assay.Particulate nitrogen and its isotopic composition were measured with an elemental analyzer(Carlo Erba NC 2500) coupled with a Finnigan MAT DeltaplusXP isotope ratio mass spectrometer.Reproducibility of nitrogen isotope measurements(in terms of δ15N) was within 0.2‰.Our results showed that N2fixation rates in the south Taiwan Strait ranged from 168—1080 nmol m-3d-1with an average of 537 nmol m-3d-1.Most of the high rates were observed at subsurface layers.The depth-integrated N2fixation rates were 11—40 μmol m-2d-1with an average of(23±10) μmol m-2d-1.The distribution of the N2fixation rates showed regional variations with influence from water masses with distinctive temperature and salinity.Higher N2fixation rates were mostly observed in the regions influenced by the Kuroshio,with an average of 31 μmol m-2d-1,while lower rates occurred in the upwelling and river plume regions with an average of 15 μmol m-2d-1.This spatial distribution pattern indicated that biological N2fixation was largely impeded by the low temperature and the high concentration of dissolved inorganic nitrogen in the south Taiwan Strait.The contribution of N2fixation in the study area could be further quantified based on the δ15N signatures of suspended particles which could be significantly depleted during N2fixation.Indeed,a negative correlation between the δ15N signatures of suspended particles and N2fixation rates was observed regardless of using all data points or depth-averaged values within the water column.This indicated that15N-depleted particles were largely derived from the enhanced N2fixation,supporting the use of nitrogen isotopic composition(δ15N) of suspended particles as a potential indicator of N2fixation in the south Taiwan Strait.Further studies are needed to better elucidate the relationship between N2fixation rates and limiting elements and their chemical speciation,and thus the physical and biogeochemical controls on N2fixation in the south Taiwan Strait.国家自然科学基金资助项目(41125020;41076043;41206062); 国际海域资源调查与开发“十二五”项目(DY125-13-E-01

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

Analysis of Epistatic and QE Interaction Effects of QTLs for Grain Shape in Rice

本研究利用基于明恢86x佳辐占水稻重组自交系(rECOMbInAnT InbrEd lInE,rIl)构建的SSr遗传图谱,总标记数为131。联合两季的稻米粒长(gl)、粒宽(gW)、长宽比(l/W)表型数据,应用混合线性模型方法进行QTl定位,并作加性效应、上位效应以及加性QTl、上位性QTl与环境(QTl-by-EnVIrOnMEnT,QE)的互作效应分析。检测到粒长、粒宽和长宽比的加性效应QTlS分别为6个、4个和4个,贡献率分别为23.67%、21.41%和25.78%;检测到8对粒长的上位性QTlS,5对粒宽的上位性QTlS,2对长宽比的上位性QTlS,贡献率分别为16.75%、22.36%和7.55%;环境互作检测中,发现共有9个加性QTlS和7对上位性QTlS与环境发生了互作。结果表明,上位效应在粒形性状的遗传与加性效应一样起了重要作用,环境互作效应对粒形性状有一定的影响。A linkage map consisting of 131 markers was constructed by using a recombinant inbred line (RIL) population derived from the indica-indica rice cross Minghui86×Jiafuzhan.Quantitative trait loci (QTLs) was located with a mixed linear model (QTLmapper1.6) based on the grain shape parameters such as grain length (GL), grain width (GW) and length-width ratio (L/W), and made analysis of additive effects, epistatic, and the interaction effects of QTL-by-environment (QE).Six, four and four QTLs were detected to have significant additive effects for GL, GW and L/W, and the contribution rate were 23.67%、21.41% and 25.78%, respectively.Eight, five and two pairs of epistatic QTLs with significant additive-by-additive (AA) interaction effects were identified for three traits, and the contribution rate were 16.75%、22.36% and 7.55%, respectively.Significant QE interactions were found for nine additive QTLs and seven pairs of epistatic QTLs.The results indicated that the epistatic effects played an important role on the inheritance of grain shape, and the environmental factor had certain effects on the three traits.福建省自然科学基金项目(X0750053);厦门大学科技创新计划项目(XDKJCX20063004)共同资