高温气相色谱和高温气相色谱-质谱法对费托合成蜡的分离和鉴定

费托合成蜡是费托合成反应中的重要产物之一。采用高温气相色谱与冷柱头进样相结合的方式,建立了一种分离分析费托合成蜡的气相色谱方法。该方法无需对费托合成蜡进行预处理,使用氦气为载气,选用更长的高温色谱柱,具有平稳的色谱基线,对费托合成蜡中正构烷烃和其他未知组分有很好的分离效果,能够洗脱费托合成蜡中碳数大于C₉₀的重组分。用高温气相色谱-质谱法对费托合成蜡馏分进行定性分析,其组分有烷烃、烯烃和含氧化合物。该方法对了解费托合成蜡组分的详细信息和费托合成工艺的开发有重要意义。     

费托合成钴基催化剂微观结构研究进展

费托合成可将煤、天然气及生物质等各种非石油含碳资源通过合成气转化为各种油品和精细化学品.钴基催化剂因其水煤气变换反应活性低、费托反应活性高、碳链增长能力高的优良特点,在工业应用和相关科学研究上备受关注.钴基催化剂微观活性位的结构和费托反应过程中催化剂的表面吸附物等都会对F-T合成反应的产物分布以及催化性能有影响.本文分...     

高温气相色谱和高温气相色谱-质谱法对费托合成蜡的分离和鉴定（英文）

费托合成蜡是费托合成反应中的重要产物之一。采用高温气相色谱与冷柱头进样相结合的方式,建立了一种分离分析费托合成蜡的气相色谱方法。该方法无需对费托合成蜡进行预处理,使用氦气为载气,选用更长的高温色谱柱,具有平稳的色谱基线,对费托合成蜡中正构烷烃和其他未知组分有很好的分离效果,能够洗脱费托合成蜡中碳数大于C_(90)的重组分。用高温气相色谱-质谱法对费托合成蜡馏分进行定性分析,其组分有烷烃、烯烃和含氧化合物。该方法对了解费托合成蜡组分的详细信息和费托合成工艺的开发有重要意义。     

α-萘基丁二亚胺氯化镍/MAO制备双(宽)峰聚乙烯

合成了一种新型α 二亚胺镍配合物———α 萘基丁二亚胺氯化镍 ,此配合物作为催化剂在MAO的活化下催化乙烯聚合得到支化聚乙烯 ,聚合活性高达 7 18× 10 5gPE molNi·h ,1 3C NMR、FTIR测试结果表明制备的聚乙烯含有末端双键 ;GPC结果表明所制备的聚乙烯分子量呈双 (宽 )峰分布 ,其原因有两个 ,一是此催化剂能产生分子量较低的α 烯烃 ,在聚合过程中一部分α 烯烃会“就地”与乙烯原位共聚形成分子量较高的聚合物 ,二是此催化剂存在立体异构体 ,而不同异构体在MAO活化下形成的活性中心的配位环境不同 ,因而得到的聚乙烯的分子量也不同 .研究了聚合温度、聚合压力、铝镍摩尔比 (nAl nNi)对催化活性、聚乙烯分子量、支化度的影响 .聚乙烯的分子量随聚合温度的升高而下降 ,支化度增大 ,熔点则降低 .     

聚乙烯废塑料温和可控降解为燃油和聚乙烯蜡

聚乙烯是最大的合成塑料产品,其化学惰性导致难以降解.最近,黄正、管志斌等报道了交叉烷烃复分解方式进行的聚乙烯温和可控降解.使用价廉量大的低碳烷烃(如石油醚)作为反应试剂和溶剂,不同类型的聚乙烯均可实现降解.并且可以通过催化剂和反应的时间的调控,选择性生成燃油或聚乙烯蜡.     

水杨醛亚胺镍配合物催化的乙烯水相聚合

在含表面活性剂的水相体系中, 用一系列水杨醛亚胺镍配合物催化乙烯聚合, 得到了高分子量低支化度聚乙烯. 研究表明水杨醛亚胺镍配合物中苯环上取代基的电子效应和空间位阻对乙烯聚合活性和聚合物的分子量有所影响. 提高配合物酚氧环上取代基的吸电子性, 聚合活性相应增加, 但聚乙烯的分子量降低; 而增加苯胺环上取代基的空间位阻, 聚合活性和聚乙烯的分子量均增加. 粘度法测得由水相聚合得到的聚乙烯的分子量在10⁴～10⁵范围内. DSC测得该聚乙烯的结晶度在50%～70%之间, 熔点在115～137 ℃范围内. GPC分析表明用环辛二烯合镍[Ni(COD)₂]助催化乙烯, 聚乙烯的分子量分布随酚氧环上取代基电负性增加而从双峰到单峰变化, 动态流变学研究进一步说明了聚乙烯分子量及其分布的变化.     

支化聚烯烃的合成研究*

本文综述了近年来以不同催化体系合成具有不同支化拓扑结构聚烯烃的研究进展。传统的方法主要是通过乙烯自由基聚合和前过渡金属催化剂催化乙烯与希小烯烃共聚来合成支化聚乙烯。其中,原位共聚法可合成得到具有不同支化度、不同支链长度的支化聚乙烯。新发展起来的后过渡金属催化剂,不仅可以催化单一乙烯合成出支化、超支化,甚至是树枝状等一系列不同拓扑结构的聚乙烯,而且可以催化乙烯与极性单体共聚得到末端功能化聚乙烯。     

MgCl_2负载双金属复合催化剂制备宽分子量分布聚乙烯

聚乙烯的分子量和分子量分布对其熔体的流变性能和产品的力学性能有显著影响．分子量分布的变化,尤其是分子量分布末端部位的变化,都会对材料的注塑行为产生大的影响［１］．为了控制Ｚｉｅｇｌｅｒ催化剂制备的聚乙烯分子量分布而改善聚合工艺的报道很多［２～４］,工业生产中可利用多步聚合工艺来获得宽分子量分布的聚乙烯［５,６］,但这种方法工艺复杂,成本高．美国ＵＣＣ公司利用复合的ＴｉＶ和ＺｒＶ催化剂在气相法Ｕｎｉｐｏｌ工艺装置上首次成功的合成出了双峰高分子量聚乙烯产品［７,８］,由于采用Ｕｎｉｐｏｌ生产工艺…     

酚硝酮为配体的锆催化剂合成与表征及催化乙烯聚合的研究

以水杨醛与苯基羟胺缩合制备的酚硝酮为配体制备了Zr的配合物,采用IR、NMR、元素分析、质谱等表征手段对酚硝酮配体以及催化剂的结构进行了表征.研究了以酚硝酮为配体的Zr的配合物与MAO组成的催化体系催化乙烯聚合的行为.研究结果表明,该催化剂乙烯均聚活性较高且具有较好的耐温性,乙烯均聚的活性大于106g/(molZr·h),催化剂的活性随着温度的升高有较大幅度的提高且在100℃条件下活性仍无明显衰减.另外,采用凝胶渗透色谱以及示差扫描量热法对制备的一系列聚乙烯的分子量、分子量分布以及热性能进行了表征,催化得到的聚乙烯分子量可达到105,熔点在132℃左右.     

α-二亚胺镍/Cp*TiCl3复式催化剂制备双峰长支链聚乙烯

合成了一种后过渡金属镍化合物 [二 N ,N′ (α 萘基 ) 2 ,3 丁二亚胺镍二溴化物 ][C1 0 H7—NC(CH3)C(CH3)N—C1 0 H7]NiBr2 ,此化合物在MAO活化下催化乙烯聚合能得到含有末端双键的低分子量聚乙烯 ,即长链α 烯烃 .此化合物和一种单茂钛化合物五甲基环戊二烯基三氯化钛 (Cp TiCl3)所组成的复式催化剂 ,用MAO活化后两种主催化剂具有良好协同作用 ,能使单一乙烯聚合制备出双峰型长支链的聚乙烯 .1 3C NMR表明由此复式催化剂制得的聚乙烯不但含有甲基、乙基、丙基、丁基、戊基支链而且还含有相当多的长支链 (支链长度大于或等于 6 ) .催化剂的摩尔比 (Ni Ti)、Al(MAO) (Ni+Ti)摩尔比和聚合温度等聚合条件对催化活性及聚合物的结构与性能有明显影响 .GPC测试表明所得到的支化聚乙烯分子量呈双峰分布 .     

高熔点蜡合成技术的研究进展

High-melting hydrocarbon waxes (melting point: > 80 ℃), consisting of saturated alkanes with carbon numbers greater than 40, exhibit unique features including high melting points, high stability, low penetration, high viscosity, as well as good wear resistance and hardness. These features make high-melting waxes suitable for use in foods, cosmetics, materials processing, electronic machinery, national defense, aviation, medical fields, etc. Considering the fast growth of technology and the electronics industry, the world's economy relies on the production and utilization of high-quality high-melting waxes. However, most waxes in the world's current markets are prepared from mineral oils, and such commercial waxes have melting points in the range of 50–70 ℃. Considering the rapid consumption of high-melting waxes and specialty waxes, their supply insufficiency is anticipated to exceed 700000 t. High-melting waxes are divided into polyethylene (PE) wax and Fischer-Tropsch synthesis (FTS) wax, based on synthesis methodology. PE wax can be obtained via the polymerization of ethylene and can also be prepared via the thermal or catalytic cracking of plastics. PE cracking to form waxes, with the advantage of low cost, can effectively solve the problem of "white pollution" and make use of existing catalytic cracking units. However, this process results in high energy consumption to achieve waste polymer depolymerization and exhibits some drawbacks, such as a wide carbon number distribution and high impurity content in the obtained PE waxes. However, there are some new methods for synthesizing PE waxes, such as cross alkane metathesis. The FTS, which uses carbon monoxide and hydrogen as raw materials, realizes the synthesis of waxes through carbon chain growth. Although the high-melting FTS waxes display excellent performance and the technology is gradually maturing, FTS waxes with different melting points are produced by rectification of products with various carbon chain lengths. Nonetheless, PE and FTS waxes are widely used in various industries because of their excellent properties. However, their synthesis is based on petroleum and coal-derived chemical products. Biomass-derived waxes have a narrow melting range due to their precise carbon chain growth process. Based on different application demands, small biomass platform molecules can be functionalized to fabricate biomass-derived waxes with special functions. More importantly, the biomass-based synthesis route is sustainable and in-line with the global values for mitigating carbon dioxide emissions and achieving carbon neutrality. This review discusses the recent advances in the synthesis techniques for high-melting waxes, including PE waxes, FTS waxes, and biomass-derived waxes. Furthermore, the catalysts and reaction mechanisms involved in the synthesis of high-melting waxes are discussed in detail. Finally, the perspectives and trends of high-melting waxes are reviewed to promote the emergence of new processes and technical routes.      

金属硫化物基钾离子电池负极：储存机制和合成策略

Rechargeable potassium-ion batteries (PIBs), with their low cost and the abundant K reserves, have been promising candidates for energy storage and conversion. Among all anode materials for PIBs, metal sulfides (MSs) show superiority owing to their high theoretical capacity and variety of material species. Nevertheless, the battery performance of MSs is hindered by many factors such as poor conductivity, low ion diffusivity, sluggish interfacial/surface transfer kinetics, and drastic volume changes. In this review, the electrochemical reaction mechanisms, challenges, and synthesis methods of MSs for PIBs are summarized and discussed. In particular, the most common synthesis methods of MSs for PIBs are highlighted, including template synthesis, hydro/solvothermal synthesis, solid-phase chemical synthesis, electrospinning synthesis, and ion-exchange synthesis. During the potassium storage process, the two-dimensional layered MSs follow the intercalation/extraction mechanism, and the MSs with inactive metal undergo the conversion reaction, whereas the metal-active MSs follow the conversion-alloying reaction mechanism. Given the inherent properties of MSs and the reactions they undergo during cycling, when used as anodes for PIBs, such materials experience a series of problems, including poor ion-/electron-transport kinetics, structural instability, and loss of active material caused by the dissolution of discharged polysulfide products and the occurrence of side reactions. These problems can be solved by optimizing the methods for synthesizing MSs with an ideal composition and structure. The template method can precisely prepare porous or hollow-structured materials, the hydro/solvothermal method can alter the thickness or size of the material by adjusting certain synthesis parameters, and the one-dimensional-structured material obtained via electrospinning often has a large specific surface area, all of which can shorten the transport pathway for potassium ions, thereby improving the performance of the battery. The ion-exchange method affords difficult-to-synthesize MSs via anion- or cation-exchange, in which the product inherits the structure of the starting material. The solid-phase synthesis method makes it possible to combine MSs with other materials. Combinations with materials such as carbon or other MSs helps to provide sufficient buffer space for the volume expansion of MSs during cycling, while promoting electron transport and improving the potassium-storage properties of the anodes. Therefore, this review aims to highlight the current defects of MS anodes and explore the construction of their ideal architecture for high-performance PIBs by optimizing the synthesis methods. Ultimately, we propose the possible future advancement of MSs for PIBs.      

金属硫化物基钾离子电池负极：储存机制和合成策略

钾离子电池由于其低成本和丰富的钾矿产资源,在能量存储和转化领域极具应用潜力。金属硫化物理论容量高且材料种类丰富,在众多钾离子电池负极材料中表现突出。然而,金属硫化物存在的缺点,如导电性差、离子扩散率低、界面/表面传输动力学缓慢等,限制了其在储钾过程中的性能表现。在这篇综述中,我们系统的讨论和总结了金属硫化物作为钾离子电池负极的电化学反应机制、所面临的挑战和合成方法。其中,重点讨论了其常见的合成方法,包括模板法、溶剂热/水热法、固相反应法、静电纺丝法和离子交换法。这篇综述意在通过优化合成策略设计合成理想的组分和结构,来解决钾电负极材料存在的问题,最终得到高性能的钾离子电池负极材料。最后我们还对基于金属硫化物的钾离子电池负极的发展方向进行了展望。     

有机硫化合物在锂硫电池中的应用

锂硫电池具有理论能量密度高、环境友好和成本低等优点,有望成为替代锂离子电池的新一代储能系统。然而,锂硫电池充放电产物的绝缘性、可溶性多硫化锂的穿梭效应、硫正极体积膨胀及锂枝晶的不可控生长,严重影响了锂硫电池的实际容量发挥和循环稳定性。为解决上述问题,采用有机硫化合物来替代单质硫作为正极材料是有前途的策略。调控有机硫化合物的硫链、碳链及其相互作用,可改变其电化学反应过程,提高离子/电子电导,抑制穿梭效应。有机硫化合物作为电解液添加剂,可调控硫正极的反应过程并保护金属锂负极,作为聚合物电解质的改性链段可加速锂离子传导。本综述对有机硫化合物在锂硫电池的正极、电解液添加剂和固态电解质中的应用研究进展进行详细的阐述。将有机硫化合物的结构、反应机理和电化学性质联系起来,为解决锂硫电池存在的问题提供见解。最后,提出高性能有机硫化合物的设计合成和机理研究思路,以期实现可实用化的锂硫电池。     

氧化物钙钛矿的光催化研究进展：CO2还原、水裂解、固氮

At present, more than 80% of the world's energy demand is fulfilled by the burning of fossil fuels, which has caused the production of a large amount of greenhouse gases, leading to global warming and damage to the environment. The high consumption of fossil fuels every year causes the energy crisis to become increasingly serious. Finding a sustainable and pollution-free energy source is therefore essential. Among all forms of energy sources, solar energy is preferred because of its cleanliness and inexhaustible availability. The energy provided by one year of sunlight is more than 100 times the total energy in known fossil fuel reserves worldwide; however, the extent of solar energy currently used by mankind each year is minute; thus developments in solar energy are imperative. To address the urgent need for a renewable energy supply and to solve environmental problems, a variety of technologies in the field of photocatalysis have been developed. Photocatalytic technology has attracted significant attention because of its superior ability to convert clean solar energy into chemical fuels. Among the photocatalytic materials emerging in an endless stream, perovskite oxide, with the general formula of ABO₃, has great potential in the fields of solar cells and photocatalysis as each site can be replaced by a variety of cations. Furthermore, owing to its unique properties such as high activity, robust stability, and facile structure adjustment, perovskite oxide photocatalysts have been widely used in water decomposition, carbon dioxide reduction and conversion, and nitrogen fixation. In terms of carbon dioxide reduction, oxide perovskites can achieve precise band gap and band edge tuning owing to its long charge diffusion length and flexibility in composition. For the development and utilization of solar energy in the environmental field, perovskite oxide and its derivatives (layered perovskite oxide) are used as photocatalysts for water decomposition and environmental remediation. In terms of nitrogen fixation, the conventional Haber-Bosh process for ammonia synthesis, which has been widely used in the past, requires high temperature and high energy. Therefore, we summarize the recent advances in perovskite oxide photocatalysts for nitrogen fixation from the aspect of activating the adsorbed N₂ by weakening the N $ \equiv $N triple bond, promoting charge separation, and accelerating the charge transfer to the active sites to realize the photochemical reaction. Overall, this review article presents the structure and synthesis of perovskite oxide photocatalysis, focusing on the application of photocatalysis in water splitting, carbon dioxide reduction, and nitrogen fixation. This review concludes by presenting the current challenges and future prospects of perovskite oxide photocatalysts.      

电催化动力学简介（英文）

电催化过程是实现社会向可再生能源与化学品转型的主要驱动力之一。电催化动力学分析是探索反应机理和建立电催化剂构效关系行之有效的方法。本文将通过三个广泛研究的电催化反应：电化学CO₂、CO还原反应和氧还原反应,探讨Tafel分析的普遍过程、隐含假设以及需要注意的问题。此外,本文将介绍电化学反应活化参数的基本概念和关键热力学、动力学变量之间的关系。     

微波热冲快速制备二维多孔La0.2Sr0.8CoO3钙钛矿用于高效电催化析氧反应

析氧反应(OER)被认为是电解水的关键限制步骤,已被广泛作为清洁能源方式用于解决能源和环境问题。钙钛矿氧化物(ABO₃)具有可调的电子结构、高灵活性的元素组成,能在OER中表现出良好的催化活性。然而,钙钛矿氧化物的合成通常需要经历长时间的高温,极易导致金属的聚集和影响材料的本征活性。气相微波技术可以显著缩短热处理时间,从而减少相关的碳排放。这项技术不仅解决了对碳中性过程日益增长的需求,而且还增加了对合成的控制,以避免产品的不良团聚。本文采用微波热冲法快速制备了二维(2D)多孔La_0.2Sr_0.8CoO₃钙钛矿。伴随微波过程的快速熵增可以有效地暴露La_0.2Sr_0.8CoO₃结构中丰富的活性位点。此外,高能微波冲击过程可以精准地将Sr²⁺引入到LaCoO₃的晶格中,通过增加Co的氧化态来增加氧空位量。这种锶元素取代镧引入的氧空位能极大提高催化剂的本征催化活性。对于碱性电解液中的OER应用,制备的La_0.2Sr_0.8CoO₃在10 mA∙cm⁻²下展现出了360 mV的过电位,Tafel斜率为76.6 mV∙dec⁻¹。且在经历30000秒的长时间循环测试后仍能维持初始电流密度的97%。这项研究为高活性二维钙钛矿的合成提供了一种简便、快速的策略。     

金属气凝胶：可控制备与应用展望

作为多孔材料家族的最新成员之一,金属气凝胶(Metal aerogels,MAs)是完全由纳米结构金属构筑而成的一类新型气凝胶。MAs兼有金属独特的物理化学性质与气凝胶的结构特征,同时拥有高速传质通道、高导电性三维网络、自支撑性与独特的光学特性,故在电催化、表面增强拉曼散射和生物传感等领域均表现出卓越性能。然而,MAs的研究历史较短,其可控制备、构效关系探索等研究存在众多挑战性问题,距离商业化应用尚有较长的道路。因此,系统梳理MAs的研究工作,从中汲取经验与总结设计原理是极为有益的。本文将对MAs的合成策略、应用研究进行系统评述,在此基础上对本领域的挑战与机遇进行总结展望。希望招徕更多科研工作者,共同探索MAs这一年轻而前景广阔的新材料领域。     

超薄氮掺杂碳纳米片负载单原子镍用于高效电催化还原二氧化碳

将二氧化碳转化为高附加值的燃料和化学品是缓解当前能源危机和控制温室气体排放的有效策略之一,但此法受限于缺乏高活性与高选择性的电催化剂。因此,我们通过热解含镍金属有机框架结构(MOF)和二氰二胺制得负载高含量镍单原子(7.77% (w))的超薄氮掺杂二维碳纳米片用于电催化还原CO₂生成CO。研究发现高温热解能将MOF中Ni²⁺转化为Ni⁺-N-C和Ni²⁺-N-C结构,且Ni⁺-N-C含量依赖于热解温度——其含量随热解温度增加呈现火山型变化。800 ℃下,Ni²⁺到Ni⁺-N-C的转化和石墨化的C生成达到最优水平。Ni⁺-N-C结构有适宜的*CO中间体结合能,能有效地抑制析氢反应的同时还能促进CO生成。因此,800 ℃热处理制得的材料(Ni-N-C-800)催化CO₂生成CO效率最高。调节电解液浓度,能进一步优化电催化性能。当电解液(碳酸氢钾)浓度为0.5 mol·L^-1时,Ni-N-C-800的CO生成选择性在较宽电压窗口内(-0.77到-1.07 V vs. RHE)都高于90%,且具有优良的稳定性。这些结果表明,选择合适的前躯体通过调控热解温度以及氮掺杂可以有效提高镍基MOF衍生催化剂的二氧化碳电催化性能。     

一维/二维W18O49/多孔g-C3N4梯形异质结构建及其光催化析氢性能研究

提高光催化分解水制氢的效率是能量转换领域的关键挑战。本研究首先合成了二维多孔氮化碳(PCN),然后在二维PCN上原位生长了一维W₁₈O₄₉ (WO),形成了一种新型的梯形(S型)异质结。该异质结可以加快界面电荷的分离和转移,赋予WO/PCN体系更好的氧化还原能力。此外,具有多孔结构的PCN提供了更多的催化活性位点。与WO和PCN相比,20% WO/PCN复合材料具有更高的H₂产率(1700 μmol·g^-1·h^-1),是PCN (30 μmol·g^-1·h^-1)的56倍。本研究提供了一种新S型光催化剂用于光催化制氢领域。