Z型g-C3N4/WO3·H2O的制备与光催化二氧化碳还原性能

利用可见光将CO₂转化为CO和CH₄有望同时解决温室效应和能源危机。Z型光催化体系能够最大限度降低光生电子-空穴对的复合,提高光催化效率。本文采用水热合成法制备了g-C₃N₄/WO₃·H₂O (CNW-1)复合材料,通过X射线衍射、X射线光电子能谱、电镜等方法进行结构表征,探究了298 K、0.1 MPa条件下其对CO₂的可见光催化还原性能,并提出了可能的反应机理。通过调控三氧化钨结晶水含量可以实现CO和CH₄的产量调节,在反应10 h后,CNW-1具有最高的CH₄产率(0.33 μmolg^_-1),而CNW具有最高的CO产率(0.67 μmolg_-1⁾。这项研究为CO₂选择性还原为C1化合物提供了一种有效策略,同时也突出了以g-C₃N₄作为半导体构建Z型光催化体系在催化领域的应用潜力。     

致密油藏CO2驱响应性防窜体系的制备及性能

以3-二甲胺基丙胺和油酸为主剂制备具有叔胺结构的CO₂响应性单体N,N-二甲基油酸酰胺丙基叔胺(DOAPA),将其与有机反离子互配构建具有CO₂响应性的蠕虫状胶束(CO₂-TWMS)。通过体系与CO₂接触前后的电导率、化学结构和微观形貌变化表征体系的响应性,结合体系表面活性变化及致密基质/裂缝双重介质CO₂驱替与CO₂-TWMS防窜过程中的压力和采收率变化揭示CO₂-TWMS防窜性能与机制。实验结果表明,当反离子为对甲苯磺酸钠,与DOAPA的摩尔比为1:1时,CO₂-TWMS体系的黏度最大。CO₂和N₂能够刺激体系电导率在0.9ms/cm和1.95ms/cm之间可逆变化、诱导微观形貌在蠕虫状胶束和球形胶束间转换。此外,CO₂能够将体系临界胶束浓度从1mmol/L降低至0.25mmol/L,最低表面张力从30.2mN/m降低至29.1mN/m,体系在气液界面的吸附效率和效能增强,有利于胶束的形成。在致密基质-裂缝双重介质中,CO₂诱导蠕虫状胶束形成,增大驱替过程中的压差,扩大CO₂驱替波及效率,采收率提高22.6%。     

钢包用矾土尖晶石浇注料的抗渣侵蚀机理研究

利用XRD,SEM等分析手段对用后的以铝酸钙水泥和MgO-SiO₂-H₂O为复合结合剂的钢包矾土尖晶石浇注料进行表征，并对其抗渣侵蚀机理进行研究。分析结果表明：铝酸钙水泥及MgO-SiO₂-H₂O体系的复合结合剂在高温下与基质中矾土细粉、α-Al₂O₃等反应生成非晶态熔融相，使得基质的致密度提高，抑制了钢包渣向其内部的渗透；预合成及原位反应生成的镁铝尖晶石吸附渣中的Fe²⁺，导致渣中Fe²⁺的浓度降低，粘度提高，最终渣的成分转变为硅含量较高的CaO-SiO₂-Al₂O₃渣；矾土原料晶界处杂质在高温下生成的非晶态熔融相迁移至基质，其富含的TiO₂与CaO-SiO₂-Al₂O₃渣中的CaO反应生成稳定的钙钛矿，降低了渣中CaO的含量，渣的粘度进一步提高，抑制了渣向矾土尖晶石浇注料内部的持续渗透和扩散。     

CO2响应型β?环糊精材料用于稠油降粘

制备了一种环境友好型马来酸酐改性β?环糊精(MAH?β?CD),温和条件下将其与脂肪酸聚醚二胺 (JD230)静电作用合成了具有CO₂响应性的表面活性剂(MJD230)。它能与油形成稳定的水包油乳液进而有效降低溶液的表面张力。CO₂调控下,MJD230可重复用于稠油的乳化降黏和破乳。利用FT?IR对结构进行表征。通过观察降黏率和乳液粒径优化MJD230的合成条件,同时对降黏性能和稳定性进行考察。在质量分数为0.5%,油水体积比为3:7的条件下,MJD230稠油降黏率可达99.19%。利用pH值和电导率的可逆变化证明MJD230溶液对CO₂的响应性和重复性。这为表面活性剂驱油和CO₂捕集相结合提高稠油采收率提供了可行的途径。关键词：稠油;乳化;CO₂响应型表面活性剂;稠油降黏中图分类号：TQ630 文献标识码： A 文章编号：1003?5214 (2023) 05?0000?00     

双模板法CeO2/g-C3N4形貌结构特征及湿式催化性能

利用微波辅助双模板法、软模板法制备了一系列的CeO₂/g-C₃N₄复合催化材料,通过XRD、N₂吸附-脱附、XPS、SEM和TEM等方式对材料进行表征,并对其湿式催化性能进行研究。结果表明,双模板法制备的D-CeO₂/g-C₃N₄复合材料表现出立方相CeO₂和层叠g-C₃N₄的特征,比表面积和孔径较大,属于介孔结构,表面存在Ce^₃₊和Ce^₄₊,有利于氧空位的形成。加入1 g嵌段共聚物 F127,使用无水乙醇溶液为溶剂,调节混合液呈碱性,微波辐射反应120 min后得到的D-CeO₂/g-C₃N₄(7.5)样品,结构完整均匀,具有最佳形貌特征。控制反应温度75 ℃,D-CeO₂/g-C₃N₄(7.5)投加0.7 g,H₂O₂投加 0.5 mL,初始pH值为5时,100 mg/L的苯酚溶液COD去除率可达80%以上。 D-CeO₂/g-C₃N₄(7.5) 复合催化材料使用五次以后仍可达60%以上的催化降解效果。     

基于WO3-MoO3和TiO2/CdS复合电极的光电致变色器件

电致变色广泛应用于智能窗领域,但电致变色材料仍需外部电源驱动,将太阳能电池与电致变色材料结合起来的光电致变色器件可实现无需外部供电的智能变色调控。性能优异的变色阴极和光阳极是当下光电致变色器件的研究热点。通过水热法制备WO₃-MoO₃薄膜,研究其电致变色性能;通过水热法结合连续离子层沉积法制备TiO₂/CdS复合薄膜,研究其光电转换性能。最后将WO₃-MoO₃薄膜和TiO₂/CdS复合薄膜分别作为光电致变色器件的变色阴极、光阳极构建WO₃/MoO₃-TiO₂/CdS光电致变色器件。WO₃/MoO₃-TiO₂/CdS光电致变色器件具有较大的光学调制范围(630nm处为41.99%)、更高的着色效率(35.787%),将其作为智能窗应用在现代建筑、通行工具等领域具有重要应用价值。     

Cu2O/rGO复合材料修饰阴极强化MFC产电脱氮性能及其机理

微生物燃料电池(MFC)在处理含硝酸盐(NO_3^--N)废水时具有同时产电和脱氮的潜力,寻找成本低且改善其产电脱氮性能的阴极修饰材料是MFC在含氮废水处理领域应用的关键。氧化亚铜/还原氧化石墨烯(Cu₂O/rGO)复合材料具有良好的电化学性能,在替代铂基材料提高MFC性能方面具有一定的应用前景。本研究通过还原法制备了Cu₂O/rGO复合材料,并对材料的结构和氧还原性能进行表征；同时,将其负载于阴极碳布后分析其电化学性能,并通过MFC的输出电压、功率密度和NO_3^--N的去除率探究Cu₂O/rGO阴极对MFC产电和脱氮性能的强化作用；通过对反硝化相关酶活性和胞外聚合物的测定,探究Cu₂O/rGO阴极强化MFC性能的机理。结果表明：Cu₂O/rGO复合材料具有大量的介孔结构,能够为电子传递提供更多的通道,并且Cu₂O/rGO复合材料具有良好的氧化还原可逆性；与Pt/C阴极相比,Cu₂O/rGO阴极的交换电流密度升高33.53%,电子转移阻力降低65.53%；Cu₂O/rGO-MFC在处理NO_3^-N废水时获得的最大平均输出电压(662.54 mV)、最大功率密度(26.27 mW/cm^₂)、平均库伦效率(32.02%)和NO_3^--N去除速率(83.33 mg NO_3^--N L/h)均高于Pt/C-MFC(485.33 mV,16.98 mW/cm^₂,7.38%,41.67 mg NO_3^--N L/h)；Cu₂O/rGO复合材料通过提高MFC阴极反硝化关键酶活性和类蛋白组分含量,改善了MFC的产电和脱氮性能。     

ML-WO3/TiO2异质结的制备及其对罗丹明B的光催化降解

采用空间限域法制备了单层三氧化钨纳米片(ML-WO₃),然后将其与TiO₂复合得到ML-WO₃/TiO₂纳米材料,被用来在模拟太阳光下对罗丹明B进行光催化降解。ML-WO₃/TiO₂的组成和光学特性通过扫描电镜、透射电镜、高分辨透射电镜、X射线衍射、紫外-可见吸收光谱和光致发光光谱手段进行表征。结果证实,纳米ML-WO₃/TiO₂克服了纯TiO₂带隙较大的缺陷,在全波段太阳光表现出比ML-WO₃和TiO₂更强的吸收性能,ML-WO₃与TiO₂之间具有明显的协同效应。活性物种捕获实验表明.OH和.O_2^-自由基是RhB降解的主要活性物种。ML-WO₃和TiO₂之间构建的Z型异质结电荷转移路径能够保证光生载流子的高效分离和重组。在5次循环实验后ML-WO₃/TiO₂的光催化活性仍能接近80%,具有良好的光化学稳定性。通过高效液相色谱-质谱检测RhB的中间产物,推测了RhB可能的降解路径。     

测试——聚乙烯亚胺改性磁性膨润土对Pb2+和Cu2+的吸附性能(测试稿件)

在磁性膨润土(MBent)表面接枝聚乙烯亚胺(PEI)制备了聚乙烯亚胺改性磁性膨润土(PEI/KH560/MBent),采用FTIR、VSM、XRD、TGA、EA、SEM和EDS对其进行了表征,考察了其对水溶液中Pb_²⁺和Cu_²⁺的吸附性能。结果表明,聚乙烯亚胺已成功接枝于磁性膨润土表面,并有效提高其对Pb_²⁺和Cu_²⁺吸附量；溶液初始pH对吸附量影响较大,随着pH的增大,吸附量增加。在pH=5,溶液初始质量浓度为300 mg/L,PEI/KH560/MBent对Pb_²⁺和Cu_²⁺吸附量分别为96.21和61.08 mg/g；吸附过程符合准二级动力学模型,吸附行为符合Langmuir吸附等温模型。热力学研究表明,吸附为自发吸热过程。经过5次循环利用后,其吸附容量仍保持初始的60%以上,表明PEI/KH560/MBent具有一定的重复利用性。     

2D/2D WO3/Ag:ZnIn2S4 Z型异质结复合物的构筑及可见光催化性能

构筑Z型异质结复合物是光催化领域解决电子-空穴对复合较快的常用方法,其独特的双光子体系能高效的提升光催化速率而备受关注。本文通过水热法原位构筑二维/二维(2D/2D)WO₃/Ag:ZnIn₂S₄ Z型异质结复合物,并且利用透射电子显微镜(TEM)、X射线衍射(XRD)、X射线光电子能谱(XPS)、紫外-可见漫反射光谱(UV-Vis DRS)、光电化学(PEC)和荧光光谱(PL)对其微观形貌、物相结构、元素化学态和光电性能等进行表征分析,以及采用可见光(加λ>420 nm的滤光片)照射来评价2D/2D WO₃/Ag:ZnIn₂S₄ Z型异质结复合物光解水制氢气和光降解甲基橙(MO)的催化性能。结果表明,在2D/2D WO₃/Ag:ZnIn₂S₄ Z型异质结复合物中,随着Ag:ZnIn₂S₄的含量增加,光催化性能也显著增强。当Ag:ZnIn₂S₄的质量分数为35.0%时,复合物表现出最佳的制氢速率(158.93 μmol.g_-1^.h_-1⁾与降解速率(0.18 min_-1^),这为基于WO₃纳米片设计和构筑2D/2D Z型异质结复合物用于可见光催化制氢和污染物降解提供了新的见解。     

Modeling of catalytic gasification kinetics of coal char and carbon

Calcium- and potassium-catalyzed gasification reactions of coal char and carbon by CO₂ are conducted, and the common theoretical kinetic models for gas-carbon (or char) reaction are reviewed. The obtained experimental reactivities as a function of conversion are compared with those calculated based on the random pore model (RPM), and great deviations are found at low or high conversion levels as predicted by theory. Namely, calcium-catalyzed gasification shows enhanced reactivity at low conversion levels of <0.4, whereas potassium-catalyzed gasification indicated a peculiarity that the reactivity increases with conversion. CO₂ chemisorption analysis received satisfactory successes in both interpreting catalytic effects and correlating the gasification reactivity with irreversible CO₂ chemical uptakes (CCU_ir) of char and carbon at 300 °C. In details, calcium and potassium additions led to significant increases in CCU_ir and correspondent high reactivities of the char and carbon. Furthermore, CCU_ir of char and carbon decreased with conversion for calcium-catalyzed reaction but increased for potassium-catalyzed one, corresponded to the tendency of their reactivity. The RPM is extended and applied to these catalytic gasification systems. It is found that the extended RPM predicts the experimental reactivity satisfactorily. The most important finding of this paper is that the empirical constants in the extended RPM correlate well with catalyst loadings on coal.     

Oscillations in the oxidation of MIBK over a Pt/HFAU catalyst: role of coke combustion

The catalytic oxidation of methyl-isobutyl-ketone (MIBK) in low concentration (1340 ppm) was investigated over a Pt/HFAU catalyst. Two main reactions were observed: total oxidation into CO₂ and the formation of non-desorbed compounds (“coke”). The conversion into these products depends on the reaction temperature, high temperatures being favourable to the conversion into CO₂ and unfavourable to the conversion into coke. Oscillations in the conversion into CO₂ were observed at specific temperatures, which were explained by coke combustion.     

Use of carbon dioxide as feedstock for chemicals and fuels: homogeneous and heterogeneous catalysis

CO₂ is considered to play a key role in an eventual climate change, due to its accumulation in the atmosphere. The control of its emission represents a challenging task that requires new ideas and new technologies. The use of perennial energy sources and renewable fuels instead of fossil fuels and the conversion of CO₂ into useful products are receiving increased attention. The utilization of CO₂ as a raw material for the synthesis of chemicals and fuels is an area in which scientists and industrialists are much involved: the implementation of such technology on a large scale would allow a change from a linear use of fossil carbon to its cyclic use, mimicking Nature. In this paper the use of CO₂ as building block is discussed. CO₂ can replace toxic species such as phosgene in low energy processes, or can be used as source of carbon for the synthesis of energy products. The reactions with dihydrogen, alcohols, epoxides, amines, olefins, dienes, and other unsaturated hydrocarbons are discussed, under various reaction conditions, using metal systems or enzymes as catalysts. The formation of products such as formic acid and its esters, formamides, methanol, dimethyl carbonate, alkylene carbonates, carbamic acid esters, lactones, carboxylic acids, and polycarbonates, is described . The factors that have limited so far the conversion of large volumes of CO₂ are analyzed and options for large‐scale CO₂ catalytic conversion into chemicals and fuels are discussed. Both homogeneous and heterogeneous catalysts are considered and the pros and cons of their use highlighted. © 2013 Society of Chemical Industry     

Hydrogenation of phenol with supported Rh catalysts in the presence of compressed CO2: Its effects on reaction rate, product selectivity and catalyst life

Hydrogenation of phenol to cyclohexanone and cyclohexanol in/under compressed CO₂ was examined using commercial Rh/C and Rh/Al₂O₃ catalysts to investigate the effects of CO₂ pressurization on the total conversion and the product selectivity. Although the total rate of phenol hydrogenation with Rh/C was lowered by the presence of CO₂, the selectivity to cyclohexanone was improved at high conversion levels >70%. On the other hand, the activity of Rh/Al₂O₃ was completely lost in an early stage of reaction. The features of these multiphase catalytic hydrogenation reactions using compressed CO₂ were studied in detail by phase behavior and solubility measurements, in situ high-pressure FTIR for molecular interactions of CO₂ with reacting species and formation/adsorption of CO on the catalysts, and simulation of reaction kinetics using a simple model. The CO₂ pressurization was shown to suppress the hydrogenation of cyclohexanone to cyclohexanol, improving the selectivity to cyclohexanone. The formation and adsorption of CO were observed for the two catalysts at high CO₂ pressures in the presence of H₂, which was one of important factors retarding the rate of hydrogenation in the presence of CO₂. It was further indicated that the adsorption of CO on Rh/Al₂O₃ was strong and caused the complete loss of its activity.     

Exploring the Effects of the Interaction of Carbon and MoS2 Catalyst on CO2 Hydrogenation to Methanol

Hydrogenation of CO₂ to form methanol utilizing green hydrogen is a promising route to realizing carbon neutrality. However, the development of catalyst with high activity and selectivity to methanol from the CO₂ hydrogenation is still a challenge due to the chemical inertness of CO₂ and its characteristics of multi-path conversion. Herein, a series of highly active carbon-confining molybdenum sulfide (MoS₂@C) catalysts were prepared by the in-situ pyrolysis method. In comparison with the bulk MoS₂ and MoS₂/C, the stronger interaction between MoS₂ and the carbon layer was clearly generated. Under the optimized reaction conditions, MoS₂@C showed better catalytic performance and long-term stability. The MoS₂@C catalyst could sustain around 32.4% conversion of CO₂ with 94.8% selectivity of MeOH for at least 150 h.     

Facile Construction of Carboxyl-Functionalized Ionic Polymer towards Synergistic Catalytic Cycloaddition of Carbon Dioxide into Cyclic Carbonates

The development of bifunctional ionic polymers as heterogeneous catalysts for effective, cocatalyst- and metal-free cycloaddition of carbon dioxide into cyclic carbonates has attracted increasing attention. However, facile fabrication of such polymers having high numbers of ionic active sites, suitable types of hydrogen bond donors (HBDs), and controlled spatial positions of dual active sites remains a challenging task. Herein, imidazolium-based ionic polymers with hydroxyl/carboxyl groups and high ionic density were facilely prepared by a one-pot quaternization reaction. Catalytic evaluation demonstrated that the presence of HBDs (hydroxyl or carboxyl) could enhance the catalytic activities of ionic polymers significantly toward the CO₂ cycloaddition reaction. Among the prepared catalysts, carboxyl-functionalized ionic polymer (PIMBr-COOH) displayed the highest catalytic activity (94% yield) in the benchmark cycloaddition reaction of CO₂ and epichlorohydrin, which was higher than hydroxyl-functionalized ionic polymer (PIMBr-OH, 76% yield), and far exceeded ionic polymer without HBDs groups (PIMBr, 54% yield). Furthermore, PIMBr-COOH demonstrated good recyclability and wide substrate tolerance. Under ambient CO₂ pressure, a number of epoxides were smoothly cycloadded into cyclic carbonates. Additionally, density functional theory (DFT) calculation verified the formation of strong hydrogen bonds between epoxide and the HBDs of ionic polymers. Furthermore, a possible mechanism was proposed based on the synergistic effect between carboxyl and Br⁻ functionalities. Thus, a facile, one-pot synthetic strategy for the construction of bifunctional ionic polymers was developed for CO₂ fixation.     

Amino Functionalized Nano Fe3O4@SiO2 as a Magnetically Green Catalyst for the One-Pot Synthesis of Spirooxindoles Under Mild Conditions

(3-Aminopropyl)-triethoxysilane attached to Fe₃O₄@SiO₂ nanoparticles has been characterized by powder X-ray diffraction, vibrating sample magnetometer, scanning electronic microscope, transmission electron microscope, energy dispersive X-ray, thermal gravimetric analysis, and Fourier transform infrared spectroscopy. The prepared nanoparticles employed as a heterogeneous catalyst in the synthesis of spirooxindoles derivatives in one-pot four-component reactions of isatin, methyl cyanoacetate or malononitrile, hydrazine hydrate, and ethyl acetoacetate. Amino-functionalized magnetic nanoparticles showed high catalytic activity in mild reaction conditions and excellent yields of products in short reaction times. Also, this nanocatalyst can be easily recovered by a magnet and reused for subsequent reactions for at least 5 times without noticeable loss in catalytic activity.     

水相介质中CO2的水合转化效应及皮肤护理应用

碳酸是一种生物效应分子，在皮肤护理方面具有重要的应用前景。CO₂在水相介质中的水合转化效应是形成碳酸的关键，然而影响其水合转化的因素尚未得到全面研究。以护理性化妆品为研究基础，分别讨论了化妆品中常用原料在水相环境下对CO₂水合转化效应的影响；讨论了CO₂极简配方体系的细胞相容性和人体功效性。结果表明，CO₂水合转化效应基本随流变调节剂黏度的增加而降低，随离子强度增强而降低；多元醇和乳化剂分子对CO₂水合转化的影响根据不同分子的性质各有不同。此外，CO₂对人角质形成细胞呈现优良的细胞相容性，含CO₂的化妆水与未涂抹样品的皮肤(对照组)相比下调了皮肤pH(由5.5到4.7)，提升了皮肤水分含量(由27%到60%)。     

Slurry-phase CO2 hydrogenation to hydrocarbons over a precipitated Fe-Cu-Al/K catalyst: Investigation of reaction conditions

The hydrogenation of CO₂ to hydrocarbons over a precipitated Fe-Cu-Al/K catalyst was studied in a slurry reactor for the first time. Reducibility of the catalyst and effect of reaction variables (temperature, pressure and H₂/CO₂ ratio of the feed gas) on the catalytic reaction performance were investigated. The reaction results indicated that the Fe-Cu-Al/K catalyst showed a good CO₂ hydrogenation performance at a relatively low temperature (533 K). With the increase of reaction temperature CO₂ conversion and olefin to paraffin (O/P) ratio in C₂-C₄ hydrocarbons as well as the selectivity to C₂-C₄ fraction increased, while CO and CH₄ selectivity showed a reverse trend. With the increase in reaction pressure, CO₂ conversion and the selectivity to hydrocarbons increased, while the CO selectivity and O/P ratio of C₂-C₄ hydrocarbons decreased. The investigation of H2/CO₂ ratio revealed that CO₂ conversion and CH₄ selectivity increased while CO selectivity and O/P ratio of C₂-C₄ decreased with increasing H₂/CO₂ ratio.     

Analytical Approach to estimate and Predict the CO2 Reforming of CH4 in a Dielectric Barrier Discharge

CO₂ reforming of CH₄ to syngas was investigated in a coaxial dielectric barrier discharge reactor immersed in an oil bath. An analytical model was suggested to estimate and predict the reaction phenomena. The model had input parameters as predictor variables (applied voltage, ratio of CH₄/CO₂, and total flow rate in the feed), output parameters as observed variables, the molar flow rates of reactants (CH₄, CO₂, CO, H₂, and by-products), and energy efficiencies. More than 70% of the output parameters variance could be explained by the input parameter. The model for the CO₂ reforming of CH₄ in a dielectric barrier discharge reactor would be useful to optimize the experiments. A comparison between input parameters suggests that the reaction should be performed under high total flow rate or low applied voltage to obtain greater energy efficiency; whereas at high applied voltage and total flow rate, the reaction obtains a greater absolute amount of reactant conversion and products, but lower energy efficiency.