PdCoNi nanoparticles supported on nitrogen-doped porous carbon nanosheets for room temperature dehydrogenation of formic acid

The development of cost-effective heterogeneous catalysts for the dehydrogenation of formic acid (FA) is the key challenge for the commercialization of FA as a hydrogen-storage medium. Herein, PdCoNi nanoparticles (NPs) with different element ratios supported on N-doped carbon nanosheets (N-CN) were designed, which exhibit excellent catalytic dehydrogenation performance for FA. Compared with PdCoNi NPs loaded on the carbon nanosheets (CN), the introduction of pyrrolic N to CN induces the formation of ultrafine, monodispersed and amorphous Pd_0.6Co_0.2Ni_0.2 NPs with a size of 1.60 nm, which significantly increases the number of active sites and the instant contact between FA and catalysts. The as-prepared Pd_0.6Co_0.2Ni_0.2/N-CN catalyst shows more than 99% conversion and 100% H₂ selectivity at room temperature, with a record-high initial turnover frequency (TOF_initial) of 1249.0 h⁻¹ among non-noble containing Pd-based catalysts, which demonstrates the high potential of Pd_0.6Co_0.2Ni_0.2/N-CN as a practical catalyst for the hydrogen generation from FA.     

Investigation of the role of Nb on Pd−Zr−Zn catalyst in methanol steam reforming for hydrogen production

Methanol steam reforming is regarded as a very promising process to generate H₂ suitable for fuel cells. Typically, the Pd-based catalysts can catalyze efficiently methanol steam reforming for hydrogen production. But their high selectivity to CO, a byproduct of methanol reforming reaction, severely limits their potential application. In this work, a series of Nb-modified Pd−Zr−Zn catalysts with different Nb loadings were prepared to study their catalytic activities with more focus on the role of Nb on Pd−Zr−Zn catalyst for methanol steam reforming. The prepared catalysts were fully analyzed by using various characterization techniques, for example, ICP, BET, SEM, XRD, H₂-TPR, NH₃-TPD, HRTEM, CO chemisorption, XPS, and Raman. The experimental results showed that an increase in Nb loading for the Nb-modified Pd−Zr−Zn catalysts led to a decrease of the methanol conversion and H₂ production rate. This was probably due to the decrease in the amount of oxygen vacancies on the catalyst surface. However, introduction of Nb into Pd−Zr−Zn catalyst increased the acid strength on the catalytic surface. The aldehyde species derived from methanol decomposition were readily transformed to HCOOH, thus yielding high selectivity to CO₂ for the Nb-modified Pd−Zr−Zn catalysts. Significantly, the addition of Nb to Pd−Zr−Zn catalyst facilitated the incorporation of Pd into the ZnO lattices, which led to the formation of Pd−Zn alloy. Consequently, the Nb-modified Pd−Zr−Zn catalysts exhibited significantly lower CO selectivity and production rate than the Pd−Zr−Zn catalyst. From the results, this work offers a new way to the rational design of selective methanol steam reforming catalysts to decrease the formation of byproduct CO.     

Synthesis of highly active and stable Pd/C catalysts toward HCOOH dehydrogenation by a simple NH3 adsorption method

Pd catalysts supported on activated carbon (Pd/C–NH₃) toward HCOOH dehydrogenation were prepared by a simple adsorption method using ammonia (NH₃) and Ar as the working gas. The results show that the TOF_initial of Pd/C–NH₃ was 459.8 h⁻¹ at 50 °C. When the reaction was carried out for 4 h, the HCOOH dehydrogenation ratio over Pd/C–NH₃ was about 81.2%, which was 1.15 and 1.13 times, respectively, as that of the as-prepared Pd/C catalyst without any treatment (Pd/C–As) and the Pd/C catalyst purchased from Sigma-Aldrich (Pd/C-CM). The total amount of H₂ and CO₂ produced by using Pd/C–NH₃ to decompose HCOOH in the third cycle was 99.4% of the gas produced by the first reaction cycle, and 1.80 and 12.60 times, respectively, as that of Pd/C–As and Pd/C-CM. The characterization results indicated that the Pd active species in Pd/C–NH₃ migrated to the outer surface of the carbon support during the reaction, and the pore volume of the carbon support became larger, which were beneficial to the reaction. These factors made Pd/C–NH₃ exhibit excellent HCOOH dehydrogenation activity and stability. NH₃ adsorption is a simple and effective method for preparing high-performance Pd/C HCOOH dehydrogenation catalysts, and has important guiding significance for the preparation of other carbon supported noble metal catalysts.     

基于堆叠分类器的心电异常监测模型设计

针对传统的人工监测心脏疾病的方法对资深医生的依赖性强,需要一定的先验知识,且其监测疾病的速度和准确性有待提高等问题,提出了一种基于堆叠分类器的心电（ECG）监测算法来用于心脏异常的判定。首先,将多种机器学习算法的优势相结合,通过叠加分类器的方式集成起来,从而弥补了单个机器学习算法学习的局限性;其次,使用合成少数过采样技术（SMOTE）对原有的数据集进行了数据扩充,使得各种疾病的数量持平从而增强数据的平衡性。通过在MIT-BIH数据集上与其他机器学习算法的结果进行比较评估,实验结果表明所提算法能够提高ECG异常监测的准确性。     

Performance of the ZrO2 promoted CuZnO catalyst supported on acetic acid-treated MCM-41 in methanol steam reforming

ZrO₂-promoted CuZnO catalysts were prepared through the sol-gel, conventional impregnation and modified impregnation methods using MCM-41 as support material and applied to the methanol steam reforming (MSR) reaction. The synthesized catalysts were characterized by the XRD, BET, FESEM, TEM, XRF, FTIR, H₂-TPR and TGA methods. The determined physiochemical properties suggested that pretreatment of MCM-41 with acetic acid before metal impregnation remarkably decreases the size of the metal particles and improves their dispersion and reduction behavior. Among the synthesized catalysts, the CuZnOZrO₂/MCM-41 sample prepared through the modified impregnation method exhibited the best catalytic performance with 97.8% methanol conversion, 99.0% H₂ selectivity, 0.4% CO selectivity and the lowest level of coke deposition, at 300 °C. In addition, all catalysts resisted against deactivation by conserving their catalytic activity over 40 h operation, indicating that the use of high surface area MCM-41 as support, the ZrO₂ promoter, and the proper synthesis methods significantly enhanced the catalytic activity in the MSR process.     

Characteristics of nylon 6,6/nylon 6,6 grafted multi-walled carbon nanotube composites fabricated by reactive extrusion

Nylon 6,6 composites containing nylon 6,6 grafted multi-walled carbon nanotubes (nylon 6,6-g-MWCNT) were fabricated from nylon 6,6 and acyl chloride grafted MWCNT (MWCNT–COCl) by reactive extrusion. MWCNT–COCl was produced by reacting acid-treated MWCNTs with thionyl chloride. Formation of nylon 6,6-g-MWCNT by reactive extrusion was confirmed by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, thermogravimetric analysis, and scanning electron microscopy. To quantify the interfacial adhesion energies of nylon 6,6 and pristine and functionalized MWCNTs, the contact angles of cylindrical drop-on-fiber systems were determined using the generalized droplet shape analysis. The interfacial adhesion energy of the nylon 6,6/nylon 6,6-g-MWCNT composite was twice that of the nylon 6,6/pristine MWCNT composite. Nylon 6,6-g-MWCNTs exhibited excellent dispersion in the composite, whereas pristine MWCNTs exhibited poor dispersion when composite films were prepared by solvent casting. The reinforcement level of the composite increased with increasing MWCNT content. Among the composites examined, the nylon 6,6/nylon-g-MWCNT composite with a fixed MWCNT content exhibited the highest level of reinforcement.     

Effect of ternary alloying elements addition on atomic ordering characteristics of Fe–Al intermetallics

The energetic and structural characteristics of atomic ordering processes in Fe_0.5(Al_1−nX_n)_0.5 intermetallics have been qualitatively analyzed based on the statistico-thermodynamical theory of ordering by means of a quasi-chemical method combined with electronic theory in the pseudopotential approximation. The effects of ternary impurities on order–disorder phase transformation temperature and the characteristics of atomic short-range order in Fe–Al type intermetallics have been calculated. Impurity elements in Fe_0.5(Al_1−nX_n)_0.5 where X=Ni, Co, Mn, Cr, Ti, Si, Zr, Hf, Nb, Ta, Re, Mo or W, are considered up to 1 at.% concentration. The results of the calculation indicate that the impurity elements, X, with regard to their lattice site occupancy characteristics (SRO) can be divided into two groups; X_I=Ni, Co, Mn or Cr element atoms substitute mainly for Al sublattice sites, whereas X_II=Ti, Si, Zr, Hf, Nb, Ta, Re, Mo or W element atoms substitute preferentially for Fe sublattice sites in Fe_0.5(Al_1−nX_n)_0.5 intermetallics. It has been found that the absolute values of partial ordering energies of the W^Al–X(R₁) and W^Fe–X(R₁) have a profound effect on the order–disorder transition temperature of Fe_0.5(Al_1−nX_n)_0.5 alloys that would either increase or remain unchanged depending on the type and content of the ternary substitutional alloying elements. The impurities X=Zr, Hf, Nb, Ta, Re, Mo or W which are preferentially distributed Fe sublattice sites are more effective in increasing order–disorder transition temperature in Fe–Al(B2) intermetallics. The results of the present calculation are in good qualitative agreement with experimental observation for most of the third component impurity elements X in Fe_0.5(Al_1−nX_n)_0.5 intermetallics.     

Activating the Pd-Based catalysts via tailoring reaction interface towards formic acid dehydrogenation

Formic acid dehydrogenation (FAD) offers an ideal route for hydrogen production, where searching for efficient and selective catalysts is imperative. However, the current state-of-the-art Pd-based metallic catalysts severely suffer from low catalytic efficiency and self-poisoning, owning to the FA dehydration side reaction. In this work, we design PANI-Pd/C composite catalysts via interfacial microenvironment regulation technique. The as-prepared 0.01-PANI-Pd/C catalyst exhibits high turnover frequency (TOF, 5654 h⁻¹) and excellent resistance to CO poisoning. The merit of polyaniline can be ascribed to: a) construction of abundant Pd–PdO interfaces; b) capturing H⁺ and accelerating the formation of the reactive species.     

基于空间近邻查询的移动医疗呼叫算法

随着大数据时代的到来，传统的计算机因为单机资源有限、运行速度慢、分布式处理支持差，已满足不了现行的医疗体系中的大数据处理需求，基于时空数据的移动医疗呼叫系统方法可以很好地解决这些问题。在移动云计算环境下研究[k]最近邻查询算法是当前一个热点问题，支持可扩展和分布式的空间数据索引对于kNN查询的效率影响很大，目前已有的查询算法不适合并行化或者会导致内容冗余。将MapReduce分布式处理技术与空间kNN查询方法相结合，设计可以快速检索到满足用户查询需求的医生位置信息的移动医疗呼叫算法。提出并构建了一个新的分布式空间数据索引方法：倒排Voronoi图索引，它将倒排索引和Voronoi图索引进行结合；提出了一种基于MapReduce的利用Voronoi图来处理kNN查询的高效算法，其在分布式环境下可以有效提高查询效率；用真实的和仿真的数据集来进行大量实验评估，实验结果表明所提出的方法具有良好的高效性和可扩展性。     

无线体域网隐私保护机制研究综述

无线体域网（WBAN）是由若干可穿戴或可植入设备及其传输节点、处理节点组成的网络结构,是当前医疗物联网重要应用方向之一。网络中的设备收集用户生理数据,通过无线技术将其发送到远端的医疗服务器,然后医疗服务提供商则通过网络访问服务器,从而为佩戴者提供服务。然而,鉴于无线网络的开放性和移动性,若WBAN中的信息被窃取、伪造或在信道中受到攻击,轻则泄露佩戴者隐私,重则危害用户的人身安全。对WBAN中隐私保护机制相关技术研究进行综述,在分析该网数据传输特点的基础上,总结了基于认证、加密和生物信号的隐私保护机制,并比较了它们的优缺点,从而为在WBAN应用中提高防范意识、改进防范技术提供参考。