Study of Co-decorated MWCNTs-promoted CuO-ZnO-ZrO2 Catalyst for Methanol Synthesis from CO2 Hydrogenation

为了改善气候条件并解决碳资源问题，需要开发能将CO2转化为有价值材料的技术。在所考虑的多种选项中，甲醇因其是重要化工原料并可作为石油补充替代合成燃料，因而通过加氢将CO2转化为甲醇的研究倍受关注。 CO2是最稳定的化合物之一。从CO2加氢制甲醇（CO2+3H2=CH3OH+H2O，G523K=46.5kJ/mol）较之从CO加氢制甲醇（CO+2H2=CH3OH，G523K=26.9kJ/mol）在热力学上不利得多。在工业上要求的反应温度（523K）下CO2加氢的平衡转化率相当低。因此，开发能在高原料气空速条件下操作的高效催化剂（以便实现高的单程甲醇时空产率），...Hydrogenation of carbon dioxide has been considered as one of the most economical and effective ways to chemically fix huge amount of emitted CO2. In order to improve climate conditions, it is desirable to develop methods to convert CO2 into valuable chemicals. Among the options considered, catalytic hydrogenation of CO2 to produce methanol has received much attention. Since carbon dioxide is on...学位：工学硕士院系专业：化学化工学院化学工程与生物工程系_工业催化学号：2062006115205

Test Method Study on Printed Circuit Board Cleanness

对离子色谱法检测印刷电路板清洁度的IPC(电子电路互连和包装标准)方法做出了进一步改进,提出了水浴加热联合氮吹样品的前处理方法,有效的去除了异丙醇对测量的干扰,而且对样品进行了浓缩;对样品中的有机酸进行了有效的分离和检测。结果表明,该前处理方法干扰小,可以使检测结果更准确,检测限为3 ng/mL(以Cl–计)。The IPC’s test method on cleanness of printed circuit board were improved.Water bath-heater combined with nitrogen-blow was proposed as a disposal method of sample.Interference of isopropanol on measure was removed effectively,and the sample was concentrated.Weak organic acids in the sample were separated effectively and examined successfully.The results show that this disposal method could make the result more exact,and its interference is small.The detection limit is 3 ng/mL(Cl–).国家自然科学基金资助项目(20527005

Kilogram Scale-up Preparation of Catalysts and its Reaction Process in Syngas Methanation

甲烷化催化剂是煤制合成天然气核心技术之一,因此研发合成气完全甲烷化催化剂具有重要意义。研究工作采用实验室小试共沉淀制备甲烷化催化剂的最佳工艺条件; 方法,进行单批次1、5和10; kg级(代号cat-1、cat-5、cat-10)催化剂的制备研究。研究了催化剂制备的控制因素和放大制备催化剂的反应性能及催化反应工艺条件。研究; 显示:催化剂制备的控制因素主要包括Na~+含量及晶型结构;放大制备催化剂具有良好的活性、操作稳定性和耐热性能,与小试制备催化剂具有较好的一致性;; 放大制备催化剂(cat-10)在所考察的还原温度、反应H_2/CO比和10000~40000; mL·h~(-1)*g_(cat)~(-1)反应空速范围内具有良好的甲烷化活性。研究结果表明,该研究单批次公斤级催化剂放大制备是成功的,为实现催; 化剂进一步放大制备提供了良好基础。Methanation catalysts play a vital role in the production of synthetic; natural gas (SNG) from coal. Based on bench-scale optimum; co-precipitation conditions of catalyst preparation, scale up; preparation of catalysts for syngas methanation with single batch of 1,; 5 and 10 kg is studied. Factors affecting catalyst; preparation/performance and scale-up were investigated. The results show; that Na~+ content and crystal structure of the catalysts are the; critical factors, and the catalysts prepared under scale-up conditions; possess excellent operation stability and heat resistance, with; consistent performance as those from bench-scale samples. The 10 kg; batch has good reaction activity under studied conditions. Therefore,; the scale-up preparation is successful for the methanation catalyst in; this study, which is useful for future scale-up preparation of related; catalysts

菊芋块茎制高果糖浆的研究

通过菊芋干片与菊粉提取液的制备、菊粉酶解、精制生产高果糖浆，菊粉酶解的适宜条件为：底物糖浓度12%，加酶量26u/g糖，PH5.0-5.5，最适温度为50℃，酶解6H，底物降解率可达98.5%。菊粉酶解液经活性炭脱色、离子交换树脂处理、减压浓缩等步骤，制得糖浆的固形物含量为73.8%，果糖含量（占固形物）为83.6%，同时对糖浆的dE值、色度、灰分、微生物含量等指标进行了测定

Successive modification of polydentate complexes gives access to planar carbon-and nitrogen-based ligands

以碳和氮为键合原子的多齿螯合物是配合物家族中非常重要的一类。具有更高齿数的平面构型NC螯合物实例相对较少，代表性的例子为四齿金属碳卟啉类化合物，这类螯合物以其独特的结构和丰富的物理化学性质引起广泛关注。然而平面五齿、六齿的NC螯合物由于几何构型“拥挤”导致合成难度高，该工作从含三元环内金属卡宾结构的CCCC型碳龙配合物出发，利用经典有机反应（炔烃对金属卡宾的插入反应），成功地实现了CCCCN/NCCCN型平面五齿螯合物的合成。这一研究为高配位型螯合物的合成提供了新思路并为平面五齿螯合物家族添加新成员。特别是，这些高配位型螯合物在可见光和近红外区域均有较好的吸收，表现出良好的光声成像、光热转换及声动力学性能。 该研究工作在张弘教授指导下完成，第一作者为iChEM博士后周小茜。该工作充分体现了多学科协同研究优势：相关化合物的合成、表征及理论计算工作由周小茜博士完成；声动力学性能研究由厦门大学公共卫生学院庞鑫博士及刘刚教授完成；光声成像研究由厦门大学公共卫生学院聂立铭教授完成。iChEM fellow卓庆德博士、博士生卓凯玥、陈志昕参与了部分实验工作。夏海平教授、香港科技大学林振阳教授和南京大学朱从青教授对研究工作给予了大力支持。【Abstract】Polydentate complexes containing combinations of nitrogen and carbon (N and C) ligating atoms are among the most fundamental and ubiquitous molecules in coordination chemistry, yet the formation of such complexes with planar high-coordinate N/C sites remains challenging. Herein, we demonstrate an efficient route to access related complexes with tetradentate CCCN and pentadentate CCCCN and NCCCN cores by successive modification of the coordinating atoms in complexes with a CCCC core. Combined experimental and computational studies reveal that the rich reactivity of metal-carbon bonds and the inherent aromaticity of the metallacyclic skeletons play key roles in these transformations. This strategy addresses the paucity of synthetic approaches to mixed N/C planar pentadentate chelating species and provides valuable insights into the synthesis of carbon-based high-coordinate complexes. Furthermore, the resulting complexes are the examples of organometallic species with combined photoacoustic, photothermal, and sonodynamic properties, which makes them promising for application in related areas.This research was supported by the National Natural Science Foundation of China (Nos. 21572185, 21561162001, and 81571744), the Research Grants Council of Hong Kong (N_HKUST603/15), the Excellent Youth Foundation of Fujian Scientific Committee (2018J06024), and the Fundamental Research Funds for the Central Universities (20720170065).该工作得到国家自然科学基金委、香港研究资助局、福建省自然科学基金、厦门大学校长基金的资助

A Novel Co-decorated CNT-promoted CuO-ZnO-ZrO_2 Catalyst for CO_2 Hydrogenation to Methanol

通讯作者: hb zhang@ xmu.edu.cn[中文文摘]用一种金属Co修饰多壁碳纳米管基复合材料(y%Co/CNT)作为促进剂,制备一种高效新型的y%Co/CNT促进CuO-ZnO-ZrO2基催化剂(记为CuiZnjZrk-x%(y%Co/CNT)),考察其对CO2加氢制甲醇的催化性能.实验结果显示,在组成经优化的Cu8Zn2Zr5-10%(4.5%Co/CNT)催化剂上,5.0 MPa,523 K,V(H2)∶V(CO2)∶V(N2)=69∶23∶8,GHSV=25 000 mL/(h.g)的反应条件下,CO2加氢的转化频率达4.99×10-3s-1,分别是相同条件下非促进的原基质Cu8Zn2Zr5和单纯CNT促进的对应物Cu8Zn2Zr5-10%CNT上的相应值(4.31×10-3和4.64×10-3s-1)的1.16和1.08倍;催化剂的表征结果显示,金属Co修饰CNT促进的催化剂对H2优良的吸附活化性能对CO2加氢转化频率(TOF)的显著提高起主要作用.在CO2加氢产物中甲醇的C-基选择性达97.9%,单程时空产率为699 mg/(h.g),具有实用前景. [英文文摘]A type of Co-decorated CNT-promoted CuO-ZnO-ZrO2 catalysts was developed.The catalyst displays excellent performance for CO2 hydrogenation to methanol.Over a Cu8Zn2Zr5-10%(4.5%Co/CNT) catalyst under reaction conditions of 5.0 MPa,523 K,V(H2)∶V(CO2)∶V(N2) = 69∶23∶8 and GHSV = 25 000 mL/(h·g),the observed turnover frequency(TOF) of CO2 hydrogenation,i.e.,the number of CO2-molecule hydrogenated on unit site of exposed Cu0 per second(s-1),reached 4.99×10-3 s-1.This value was 1.16 and 1.08 times that(4.31×10-3 and 4.64×10-3 s-1) of the CNT-free substrate Cu8Zn2Zr-5 and the simple CNTpromoted counterpart Cu8Zn2Zr5-10%CNT,respectively, under the same reaction conditions.The selectivity of CH3OH in the CO2 hydrogenation products reached 97.9%, with corresponding STY reaching 699 mg/(h. g).Characterization of the catalyst revealed that the excellent capability of the Co-deco rated CNTpromoted catalyst for adsorbing and activating H2 played an important ro le in facilitating the increase of rate of surface CO2 hydrogenation reactions.国家“973”项目(2005CB221403,2009CB939804

Discounting or Priority: Which Rule Dominates the Intertemporal Choice Process?

为探索跨期决策的心理机制, 本研究利用加工分离程序范式, 检验了跨期决策过程的主导策略究竟是分析系统的时间折扣策略还是启发式系统的单维占优策略。3个实验分别操纵了决策目标、认知负荷和策略启动因素, 实验结果一致性地发现:能够影响分析系统策略的决策目标和策略启动因素没有导致分析系统策略贡献率的变化, 能够影响启发式系统策略的认知负荷和策略启动因素导致了启发式系统策略贡献率的变化。研究结果支持启发式系统的单维占优策略在跨期决策中起作用的假设, 但不支持分析系统的时间折扣策略起作用的假设。本研究或能加深人们对跨期决策心理机制的理解, 并为建立、健全与跨期决策相关的政策、法律、法规提供理论支持和帮助。</p

A process test of priority models of intertemporal choice

&nbsp;跨期选择需要决策者在眼前与未来的损益之间做出权衡与取舍。主流跨期选择理论认为, 跨期选择是把未来价值折扣到现在, 根据折扣后的价值进行选择的过程; 而单维占优模型则认为决策者把&quot;结果&quot;维度上的差异和&quot;延迟&quot;维度上的差异进行比较(维度间差异比较), 然后根据差异更大的维度(即占优势的维度)进行决策。跨期选择众理论之争无果的原因之一或是研究者未能找到揭示其心理过程的令人信服的证据。为此, 本研究采用过程检验而非结果拟合的方法, 首创了&quot;直观模拟天平&quot;任务, 对维度间差异比较的大小进行测量, 从而为验证单维占优模型提供了支持性的证据。实验1A证明了维度间差异大小中介了选择结果, 被试认为&quot;结果&quot;维度上的差异相对于&quot;延迟&quot;维度上的差异越大, 越倾向于选择延迟长、结果大的选项; 反之, 被试认为&quot;延迟&quot;维度上的差异相对于&quot;结果&quot;维度上的差异越大, 越倾向于选择延迟短、结果小的选项。实验1B证明了维度间差异比较是在选择时实时(而不是在选择后)进行的。实验1C通过调整实验程序消减了共同方法偏差对结果的影响。实验2进一步证明维度间差异比较可以解释众多的跨期选择异象。通过4个实验, 本研究揭示了维度间差异比较构成了跨期选择的重要(尽管可能不是唯一)决策过程, 为支持单维占优模型提供了重要的过程验证证据。</p

CCVD法制碳纳米管用Ni-Mg-O催化剂的制备研究

用草酸盐共沉淀法制备一类固溶体型NixMg1-xO纳米催化剂.该类催化剂用于甲烷催化分解合成碳纳米管(CNTs)显示出优良的性能.催化剂的制备优化研究揭示,催化剂的金属元素组成、氧化前驱物的焙烧和还原的温度对催化剂的性能有强烈的影响.在经优化的制备条件(n(Ni)∶n(Mg)=0.5:0.5,焙烧温度873 K,H2-还原温度973 K)下制备的Ni0.5Mg0.5O催化剂上,在经优化的制管反应条件(873 K,甲烷原料气GHSV=5×104mL/(h.g))下,反应2 h的CNTs产物的产率达到14.5 g/g

A Highly Efficient Sc_2O_3-promoted Ni-ZrO_2 Catalyst for Methanation of Coal-based Syngas to Produce Synthetic Natural Gas

用SC2O3作为促进剂,研发出一种SC2O3掺杂的高效新型nI-zrO2基催化剂,该催化剂对CO和CO2共甲烷化制合成天然气(Sng)显示出高的活性和优异的热稳定性.在组成经优化的nI6zr3SC1催化剂上,0.1 MPA,573k,V(H2)∶V(CO)∶V(CO2)∶V(n2)=75∶15∶5∶5,出口空速gHSV=40 000Ml/(H·g)的反应条件下,在反应开始之后的20~332H的反应过程中,CO和CO2的转化率一直分别保持在100%和85%的高水平,产物甲烷的选择性一直保持在100%.耐热试验结果显示,在973k下经历24H甲烷化反应、而后降至573k的nI6zr3SC1催化剂试样上,(CO+CO2)的总转化率仍能稳定地保持在80.2%的水平;而不含SC2O3的原基质催化剂(nI6zr4)在经历相同耐热试验过程之后的(CO+CO2)总转化率骤降至2.7%,暗示其因烧结而失活.催化剂的表征结果证实,可观量的SC3+溶解入zrO2晶格导致具有C-zrO2结构的单一C-(zr-SC)Oy相的生成并使其稳定化,这类C-(zr-SC)Oy相与nI6zr3SC1催化剂的高活性,尤其与优良的热稳定性,密切相关.A type of highly efficient Ni-ZrO2catalysts doped with Sc2O3for co-methanation of CO and CO2 was developed,and displayed high activity and excellent thermal stability.Over a Ni6Zr3Sc1catalyst under the reaction conditions of 0.1 MPa,573 K,V(H2)∶V(CO)∶V(CO2)∶V(N2)=75∶15∶5∶5,GHSV=40 000mL/(h·g)(outlet),the observed conversion of CO and CO2maintained continuously at high levels of 100%and 85%,respectively,during 20-332hafter the reaction started,with the corresponding selectivity of CH4product being 100%.The results of heat-resisting test showed that,over the Ni6Zr3Sc1catalyst after undergoing 24h of the methanation operation at 973Kfollowed by going down to 573K,the total conversion of(CO+CO2)still maintained stable at the level of 80.2%,whereas that of the Sc2O3-free Ni6Zr4catalyst after undergoing the same heat-resisting test fell to 2.7%,implying that it was deactivated due to sintering.The results of the catalyst characterization demonstrated that solution of a considerable amount of Sc3+in the ZrO2lattice resulted in the formation of(Zr-Sc)Oy composite oxide with simple c-ZrO2phase-structure,which was closely associated with the high activity,especially the extremely high thermal stability,of the Ni6Zr3Sc1catalyst.国家重点基础研究发展计划(973)项目(2011CBA00508); 优秀国家重点实验室基金项目(20923004); 教育部创新团队项目(IRT1036