硫化CoMo/Al2O3催化剂上H2同时催化还原SO2和NO(Ⅰ)——催化剂的制备、表征及性能

用浸渍法制备了CoMo/Al2O3催化剂,并对其进行了XRD、低温氮吸附-脱附和TPR表征.结果表明,随着Co负载量的增加,催化剂表面活性物种增加,但同时催化剂的比表面积和孔容逐渐减小;硫化后的催化剂比未经硫化处理的催化剂表面具有更多更易还原的活性物种.将所制得的催化剂硫化后用于NO分解和H2还原NO反应,NO均完全转化,但催化剂最终会因为晶格硫的大量流失而活性下降.在H2还原NO反应体系中,H2的存在使得催化剂晶格硫的流失速率极大变缓,催化剂活性下降较慢;在H2同时还原SO2和NO体系中,由于晶格硫能够得到外界源源不断的补充,因此,SO2和NO能同时在催化剂表面实现稳定的还原,反应温度、空速、进料气中H2的配比、催化剂中Co负载量以及硫化预处理方式对催化剂的活性有显著影响.活性测试结果表明,在500℃,空速12000 h-1,n(H2)/n(SO2 NO)=2时,5%Co10%Mo/Al2O3上SO2和NO转化率均为100%,单质硫产率达96.6%.     

Co-Ni／SiO2催化剂催化乙酸重整制氢反应研究

用浸渍法制备了一系列Co-Ni/SiO2催化剂,利用固定床反应器对催化剂在乙酸重整制氢反应中的催化性能进行了测试,详细研究了Co-Ni配比、活性组分负载量,反应温度,空速及水碳比对催化剂活性的影响.实验结果表明,该催化剂能高效催化乙酸重整反应.当Co和Ni摩尔比例为0.5∶1,活性组分质量百分含量为15%时催化剂呈现最好的催化活性,在水碳摩尔比为7.5∶1,温度大于500℃时可使乙酸完全转化,并且氢和二氧化碳选择性均达95%以上.     

多孔不锈钢表面的陶瓷修饰及所负载的透氢钯膜

多孔基体负载的钯膜具有优异的透氢性能,可作为氢气分离器应用于产氢、氢气回收、膜催化反应器等.近年来,以多孔不锈钢为基体的钯复合膜得到了快速的发展,该种膜组件具有更好的物理强度、易于密封和安装,因而具有更高的实用性.但多孔不锈钢一般不宜直接用作钯膜基体,需要进行陶瓷修饰.本文分别介绍了多孔不锈钢、陶瓷修饰层与钯膜三个组成部分,其中重点介绍了多孔不锈钢表面的陶瓷修饰这一关键技术环节.     

石墨烯膜质子传输巨大光效应的微观机理

Graphene monolayers are permeable to thermal protons and impermeable to other atoms and molecules, exhibiting their potential applications in fuel cell technologies and hydrogen isotope separation. Furthermore, the giant photoeffect in proton transport through catalytically activated graphene membranes was reported by Geim et al. Their experiment showed that the synergy between illumination and the catalytically active metal plays a key role in this photoeffect. Geim et al. suggested that the local photovoltage created between metal nanoparticles and graphene could funnel protons and electrons toward the metal nanoparticles for the production of hydrogen, while repelling holes away from them, causing the giant photoeffect. However, based on static electric field theory, this explanation is not convincing and the work lacks an analysis on the microscopic mechanism of this effect. Herein, we provide the exact microscopic mechanism behind this phenomenon. In semi-metal pristine graphene, most photon excited hot electrons relax to lower energy states within a timescale of 10⁻¹² s, while the typical timescale of a chemical reaction is 10⁻⁶ s. Thus, hot electrons excited by incident photons relax to lower energy states before reacting with protons through the graphene. When graphene is decorated with metal, electron transfer between the graphene and the metal, induced by different work functions, would result in the formation of interface dipoles. When using metals such as Pt, Pd, Ni, etc., which can strongly interact with graphene, local dipoles form. Protons are trapped around the negative poles of the local dipoles, while electrons are around the positive poles. Upon illumination, the electrons are excited to metastable excited states with higher energy levels. Due to the energy barriers around them, the free electrons in the metastable excited states will have a relatively longer lifetime, which facilitates the production of hydrogen through their effective reaction with protons that permeated through the graphene. The concentration of high-energy electrons under illumination was estimated, and the results showed that more electrons are energized to the excited state with strong illumination. According to the analysis, the giant photoeffect in proton transport through the catalytically activated graphene membrane is attributed to long-lived hot electrons and a fast proton transport rate. Since there is no change in the activation energy of the reaction, the metal catalyst increases the rate of the reaction by increasing the number of successful collisions between the reactants to produce the significant photoeffect. This might lead to a new microscopic mechanism that clarifies the role of the catalyst in improving the efficiency of photo(electro)catalytic reactions.     

双功能复合材料g-C3N4/CdS/Ni催化光解水产氢和5-羟甲基糠醛氧化性能

采用高温煅烧法、 原位生长法和光还原法分三步制备出双功能复合光催化剂g-C₃N₄/CdS/Ni. 材料中CdS的引入可以增强光生电子和空穴的分离效率, Ni可以进一步提高光致产氢速率. 在以三乙醇胺(TEOA)为电子给体的水溶液中对所制备的材料进行了催化产氢性能测试, 并对材料中CdS的含量进行了优化. 结果表明, 25% (质量分数)CdS负载量的复合材料催化产氢性能最佳, 其催化产氢速率为4134.5 μmol·g^-1·h^-1, 是 g-C₃N₄/Ni催化产氢速率的115倍. 且Ni是一种良好的质子催化剂. 在此基础上, 以5-羟甲基糠醛(HMF)替代TEOA作为体系的电子给体, 其可以被选择性地催化氧化为增值化学品2, 5-二甲酰基呋喃(DFF). 当体系中HMF的转化率为82.3%, DFF的选择性为69.4%时, DFF的产率(57.2%)达到最高, 体系中H₂的产量为 51.8 μmol/g. g-C₃N₄/CdS/Ni复合材料可以在同一体系中进行催化光致产氢和HMF的选择性氧化.     

碳/碳化铁复合介孔材料的合成及储氢性能!

以1-氰甲基-3-甲基咪唑四氯化铁盐([MCNIm]+[FeCl4]-)为前体,SBA-15为模板,采用硬模板纳米浇筑法合成碳/碳化铁复合介孔材料.研究了合成温度和时间对所得材料比表面积的影响.利用氮气吸附-脱附、X射线衍射、透射电子显微镜及X射线光电子能谱等对材料进行表征.结果显示,在800℃下煅烧能够得到相对较大比表面积的材料,同时延长煅烧时间可以得到高比表面积、孔径分布均匀且结构较完整的材料,其最大比表面积可达517.96 m2/g.此外,氢气吸附测试表明,此种材料具有一定的储氢性能.     

带终止事件的多类型复发事件的一般加性乘积比例模型

带终止事件(例如死亡)的复发事件经常出现在医疗和日常观测中,大多数模型假定协变量效应是乘性的,并在给定生存分布条件下对事件复发率建模.在本文中,我们对带终止事件的复发事件数据建立一般加性乘积比例模型,这里所谓的终止事件就是阻止复发事件的再发生.利用估计方程法和逆概率加权方法,我们分别提出两种估计回归参数和基本均值函数的方法.并且建立了估计的渐近性质.     

一种控制化学混沌的新方法--在全混沌区的非线性人工神经网络偶然微扰反馈控制

提出了一种控制化学混沌的新方法以稳定控制不稳定周期轨道 (UPO) .这是一种偶然比例反馈控制 (OPF)战略的扩展 ,它克服了OPF局限性 ,即OPF控制律的线性限制 ,并扩展到全混沌区 .本方法利用反传人工神经网络 (BP ANN)来表达非线性控制律 ,以增加控制的鲁棒性 .其有效性通过一个混沌自催化反应模型的数值模拟进行了检验 .     

关于割圆连比例解的项氏定理探析

借用项名达易率法、借率法和明安图多项式，本文分析证明关于割圆连比例解的项氏定理，澄清了易主经法的基本原理和方法特征，揭示了易率法与借径术、还原术三者之间的关系。