不同活性焦载体对V2O5/AC催化剂脱硫活性的影响

活性焦载体的选择是制备高活性烟气脱硫催化剂的关键.以四种煤制活性焦(AC)为载体,制得了系列V2O5/AC催化剂.通过脱硫活性评价、催化氧化能力测试和孔结构分析表明,AC表面的高活性氧化位较少,担载V2O5使AC表面产生了新的高活性氧化位,其脱硫活性显著提高;V2O5在具有高比表面积和较大孔容的载体上分散性较好,能够形...     

助剂形态对Pt/γ-A12O3催化剂抗积炭性能的影响

采用CO和H2脉冲吸附、程序升温还原、NH3程序升温脱附及X射线衍射等手段对各金属氧化物改性的Pt/Al2O3催化剂进行了表征,研究了助剂形态对Pt/Al2O3催化剂在非临氢条件下催化环己烷脱氢反应性能的影响.结果表明,催化剂稳定性从高到低依次为Zr-Pt/Al2O3＞ Ca-Pt/Al2O3＞ Ce-Pt/Al2O3...     

Coke formation during the methanol-to-olefin conversion: in situ microspectroscopy on individual H-ZSM-5 crystals with different Brønsted acidity

Coke formation during the methanol‐to‐olefin (MTO) conversion has been studied at the single‐particle level with in situ UV/Vis and confocal fluorescence microscopy. For this purpose, large H‐ZSM‐5 crystals differing in their Si/Al molar ratio have been investigated. During MTO, performed at 623 and 773 K, three major UV/Vis bands assigned to different carbonaceous deposits and their precursors are observed. The absorption at 420 nm, assigned to methyl‐substituted aromatic compounds, initiates the buildup of the optically active coke species. With time‐on‐stream, these carbonaceous compounds expand in size, resulting in the gradual development of a second absorption band at around 500 nm. An additional broad absorption band in the 600 nm region indicates the enhanced formation of extended carbonaceous compounds that form as the reaction temperature is raised. Overall, the rate of coke formation decreases with decreasing aluminum content. Analysis of the reaction kinetics indicates that an increased Brønsted acid site density facilitates the formation of larger coke species and enhances their formation rate. The use of multiple excitation wavelengths in confocal fluorescence microscopy enables the localization of coke compounds with different molecular dimensions in an individual H‐ZSM‐5 crystal. It demonstrates that small coke species evenly spread throughout the entire H‐ZSM‐5 crystal, whereas extended coke deposits primarily form near the crystal edges and surfaces. Polarization‐dependent UV/Vis spectroscopy measurements illustrate that extended coke species are predominantly formed in the straight channels of H‐ZSM‐5. In addition, at higher temperatures, fast deactivation leads to the formation of large aromatic compounds within channel intersections and at the external zeolite surface, where the lack of spatial restrictions allows the formation of graphite‐like coke.     

A Solution‐Processed Air‐Stable Perylene Diimide Derivative for N‐type Organic Thin Film Transistors

For future all‐soluble organic thin film transistor (OTFT) applications, a new soluble n‐type air‐stable perylene diimide derivative semiconductor material with (trifluoromethyl)benzyl groups (TC–PDI–F) is synthesized. The film is formed by spin‐coating in air and optimized for OTFT fabrications. The transistor characteristics and air‐stability of the TC–PDI–F OTFTs is measured to investigate the feasibility of using solution‐processed TC–PDI–F for future OTFT applications. For all‐solution OTFT process applications, the transistor characteristics are demonstrated by using TC–PDI–F as an n‐type semiconductor material and liquid‐phase‐deposited SiO₂ (LPD–SiO₂) as a gate dielectric material. All processes (except material synthesis and electrode deposition) and electrical measurements are conducted in air.     

坝前淤泥土与新填坝体接触面抗剪强度试验研究及工程应用

坝前淤泥面与新填筑坝体接触面是"坝前淤泥面加坝"技术的薄弱环节。为了探究不同工况下淤泥坝基、新填筑坝体,以及淤泥土-新填土接触面的剪切强度特性,以宁夏南部山区西吉县南川水库坝前淤泥面加坝工程为研究对象,通过常规应变式直剪仪、改进常规应变式直剪仪分别进行剪切试验,分析了淤泥土含水率和压实度变化时,淤泥土、新填土、淤泥土-新填土接触界面的抗剪强度、黏聚力、内摩擦角的变化规律。试验结果表明:新填土抗剪强度最大,不同工况下淤泥土-新填土接触界面的抗剪强度介于淤泥土和新填土的抗剪强度之间;淤泥土含水率在12%~16%之间存在最优含水率,超过该含水率后,淤泥土及淤泥土-新填土接触界面之间的抗剪强度均显著降低;当淤泥土含水率从8%增加至12%、16%时,黏聚力减小8%左右后迅速减小至22%,具有明显的阶段性,而淤泥土-新填土接触界面的黏聚力呈现先增加后减小的趋势;当含水率相同时,随着压实度的增加,淤泥土、淤泥土-新填土接触面的黏聚力、内摩擦角总体呈增大趋势。最后根据试验结果对"坝前淤泥面加坝"工法的工程应用提出了相关建议。     

The Assignment of the 1600 cm−1 Mystery Band of Carbons

Abstract

The assignment of a band near 1600 cm^?1 in IR spectra of carbons has been controversial for four decades. However, many different carbons have been studied: effectively, a single band assignment was sought for an absorption appearing with three different classes of carbon. As these differ in over-all structure, not one but three explanations are needed. These are discussed. However, undue emphasis has been placed on a single absorption; attention should also be paid to other absorptions accompanying the 1600 cm^?1 band.     

镍基钙钛矿型催化剂的结构调控及其在甲烷干重整反应中的应用

钙钛矿材料在催化领域具有广泛的应用,其微观结构的调控对催化性能有显著的影响.我们采用柠檬酸配合法、溶胶凝胶法、燃烧法和浸渍法一系列不同的制备过程对镍基钙钛矿材料的结构进行调控,并将其应用于甲烷干重整反应,研究了制备方法对活性组分Ni的化学形态、Ni与基底的相互作用以及活性氧物种的调控,进而影响其催化活性和抗积碳能力.结果表明,燃烧法可以显著提高催化剂的结晶度,从而提高Ni与基底的相互作用以及表面氧物种的含量,使其具有较强的抗积碳能力.燃烧法合成的Ni基钙钛矿催化剂在CH4∶CO2=1.25∶1,800℃的条件下反应300 h后,积碳量仅为1.0%,而在同样条件下浸渍法合成的催化剂积碳量则高达14.6%.     

硫化氢对钴改性活性焦脱除煤气中汞的影响机理

采用等体积浸渍煅烧法制备钴改性活性焦(Co-AC),并采用BET、XRD等分析手段进行表征。 利用固定床吸附实验台,研究了模拟煤气(N₂、H₂、CO、H₂S)气氛下汞的吸附特性,重点关注H₂S对汞吸附的影响。 结果表明,5%负载量的Co-AC在120 ℃和H₂S作用下具有优异的脱汞能力,2 h内平均脱汞效率高达97.8%。 此外基于密度泛函理论,首先计算了H₂S、HS及S在Co₃O₄(110)表面的吸附能及键长,通过比较H—S键键长的变化得出H₂S会逐步解离成HS与S,然后将优化后的S-Co₃O₄(110)作为Hg的吸附基底,研究其吸附特性,得出Hg与S反应生成稳定的HgS,吸附能为-3.503 eV,证明了汞的吸附遵循Eley-Rideal机制。 Co-AC吸附剂在高温下脱汞性能受到极大的抑制,因为随吸附温度升高,表面活性硫的减少及硫和汞的反应平衡常数下降显著,导致汞的脱除能力下降。 本文采用了实验加模拟的手段,探明了H₂S存在时Hg⁰在钴基吸附剂表面的反应机理,为协同脱除煤气中的H₂S和Hg⁰提供了理论指导。     

固体氧化物燃料电池直接以焦炭为燃料的电性能

直接碳固体氧化物燃料电池（DC-SOFC）是一种潜在的固体碳燃料高效率、低污染发电技术。本研究报道了将工业焦炭直接用作管式DC-SOFC燃料的研究。制备了电极材料为Ag-GDC （钆掺杂氧化铈）的YSZ （钇稳定化氧化锆）电解质支撑型管式固体氧化物燃料电池（SOFC）。采用拉曼光谱、扫描电镜和X射线能谱仪对焦炭燃料进行了性质表征。结果表明,焦炭燃料呈微米级的颗粒状,并含有大量对Boudouard反应有利的缺陷结构。电池以纯焦炭为燃料在850℃取得的最大功率密度为149mW/cm²,在碳燃料表面负载能提高Boudouard反应速率的Fe催化剂后,最大功率密度提高至217mW/cm²。通过电化学测试和尾气表征,分析了恒电流放电过程中电池的性能衰减机制。测试结果证明了将焦炭直接用作全固态DC-SOFC的燃料产生电能的可行性。