常压下玉米秸秆液化工艺的优化及其生物油分析

随着化石能源的日益短缺，可再生木质生物质资源的利用越来越受到重视，常压液化技术是生物质资源高效利用的主要方式之一。利用单因素方法，探讨液化温度、复配液化剂二甘醇（DEG）与1,2-丙二醇（PG）的混合比、液固比、催化剂磷酸的用量、反应时间等因素对玉米秸秆液化得率的影响，以便优化其液化工艺；然后采用热重分析仪（TGA）、气相色谱-质谱技术（GC-MS）和核磁共振（NMR）技术对此优化条件下所得生物油的挥发降解特性和主要组成成分进行了检测探讨。分析表明，玉米秸秆液化时优化工艺参数为：液化温度170 ℃，液化剂DEG与PG混合比1∶2，液固比5∶1，H₃PO₄用量10%，反应时间45 min；此时玉米秸秆液化得率高至99.50%。TGA结果表明，此条件下所得生物油含有80%以上碳数小于25的化合物，热解后最终残炭量约为15%。GC-MS表明，可以检测出此生物油中含有的39种有机物，其中，醇类有机物的含量最多，酚类有机物的含量次之，它们相对含量依次是70.70%和25.63%，其还含有一定量的有机酸（2.80%）、醚类（0.64%）、酯类（0.10%）和酮类（0.13%）等有机物；其组分十分复杂，高含氧量，稳定性较差。1H-和13C-NMR分析表明，不同化学位移δ与生物油中不同类型的质子和碳原子相对应，明确生物油中不同类型H和C的分布，有利于对其分子结构进行深入探讨。这些研究为非木材生物质高效液化条件的选择及液化产物制备化学品和生物燃油给予理论基础与应用支持，促进了生物质资源的有效转化利用及其生物质基产品的开发。     

Asymptotic growth bounds for the 3‐D Vlasov‐Poisson system with point charges

In this article, we consider the asymptotic behavior of the classical solution to the 3‐dimensional Vlasov‐Poisson plasma interacting repulsively with N point charges. The large time behavior in terms of diameters of its velocity‐spatial supports is improved to O(t^2/3+ϵ) for any ϵ>0.     

Assessing the nucleophilic character of 2-amino-4-arylthiazoles through coupling with 4,6-dinitrobenzofuroxan: Experimental and theoretical approaches based on structure-reactivity relationships

A kinetic study of the reactions of potentially bioactive 2-amino-4-arylthiazoles with highly reactive 4,6-dinitrobenzofuroxan (DNBF) is reported herein in acetonitrile solution. The complexation reaction was followed by recording the UV–vis spectra with time at λ_max = 482 nm. Electronic effects of substituents influencing the rate of reaction have been studied using structure-reactivity relationships. It is shown that the Hammett plot relative to the reaction of DNBF with 2-amino-4-(4-chlorophenyl)thiazole exhibit positive deviation from the log k₁ versus σ correlation, while it showed excellent linear correlation in terms of Yukawa–Tsuno equation. It has be noticed that the nonlinear Hammett plot observed for 2-amino-4-(4-chlorophenyl) thiazole is not attributed to a change in rate-determining step but is due to nature of electronic effect of substituent caused by the resonance of stabilization of substrates. The second-order rate constant (k₁) relating to the bond C–C and C-N forming step of the complexation processes of DNBF with 4-substituted-aminothiazoles and 2-amino-5-methyl-4-phenylthiazole, respectively, is fit into the linear relationship log k = s_N (N + E), thereby permitting the assessment of the nucleophilicity parameter (N) of the 2-amino-4-arylthiazoles of the range (4.90 < N < 6.85). 2-amino-4-arylthiazoles is subsequently ranked by positioning its reactivity on the general nucleophilicity scale developed recently by Mayr and coworkers (2003) leading an interesting and a direct comparison over a large domain of π-, σ -, and n-nucleophiles. The global electrophilicity/nucleophilicity reactivity indexes of the 2-amino-4-arylthiazoles have been investigated by means of a density functional theory (DFT) method. .     

The self-assemblies of a newly designed star-shaped molecule end-capped with bromine atoms studied by scanning tunneling microscopy

A new star-shaped molecule StOF-Br_3 containing oligofluorenes and halogen atoms(Bromine) has been synthesized and studied by Scanning Tunneling Microscopy(STM) at the highly oriented pyrolytic graphite(HOPG) surface.We have obtained the high-resolution self-assembled STM images,from which the highly ordered and closely packed non-porous arrangements of the StOF-Br_3 molecular selfassemblies at the heptanoic acid/HOPG surface could be observed.The molecular models and selfassembled StOF-Br_3 architectures have been given in the following text.Besides,we have also figured out the surface free energy by the density functional theory(DFT) calculation,which proved that the halogen...halogen interaction was strong enough to stabilize the ordered molecular self-assemblies.This work verifies the existence of bromine...bromine interactions,and meanwhile provides a kind of effective approach for quickly building ordered molecular nanoarchitectures with large areas and different geometries.     

Mass spectrometry imaging of latent fingerprints using titanium oxide development powder as an existing matrix

Recent research has focused on increasing the evidentiary value of latent fingerprints through chemical analysis. Although researchers have optimized the use of organic and metal matrices for matrix‐assisted laser desorption/ionization‐mass spectrometry imaging (MALDI‐MSI) of latent fingerprints, the use of development powders as matrices has not been fully investigated. Carbon forensic powder (CFP), a common nonporous development technique, was shown to be an efficient one‐step matrix; however, a high‐resolution mass spectrometer was required in the low mass range due to carbon clusters. Titanium oxide (TiO₂) is another commonly used development powder, especially for dark nonporous surfaces. Here, forensic TiO₂ powder is utilized as a single‐step development and matrix technique for chemical imaging of latent fingerprints without the requirement of a high‐resolution mass spectrometer. All studied compounds were successfully detected when TiO₂ was used as the matrix in positive mode, although, generally, the overall ion signals were lower than the previously studied CFP. TiO₂ provided quality mass spectrometry (MS) images of endogenous and exogenous latent fingerprint compounds. The subsequent addition of traditional matrices on top of the TiO₂ powder was ineffective for universal detection of latent fingerprint compounds. Forensic TiO₂ development powder works as an efficient single‐step development and matrix technique for MALDI‐MSI analysis of latent fingerprints in positive mode and does not require a high‐resolution mass spectrometer for analysis.     

An investigation of paddle wheel Cu2(μ2-O2CCH3)4 for gas molecule adsorptions

Metal organic frameworks (MOFs) have been well-known and extensively researched due to the high storage /good selectivity for gas molecules. Herein, the structures and electron paramagnetic resonance (EPR) spectra for dicopper paddle wheel MOF compound (Cu₂(µ₂-O₂CCH₃)₄ with various gas molecule are theoretically investigated by density functional theory (DFT) calculations. The adsorption energies and isotherms (including pure gas molecules and the mixed ones) are calculated for the gas molecules interacting with the unsaturated Cu₂(µ₂-O₂CCH₃)₄. Both quantities exhibit the roughly consistent orders (e.g. H₂S?>?NH₃?>?CO₂?>?CO?>?H₂O?>?N₂?>?NO?>?H₂ for isotherms and H₂S?>?NH₃?>?N₂?>?CO₂?>?NO?>?H₂O?>?H₂?>?CO for adsorption energies), possibly suggesting that this material may act as a potential adsorbent of these gas molecules. The catalytic property of Cu₂(µ₂-O₂CCH₃)₄ for oxidation of CO and NO into non-toxic molecules and splitting of H₂O into H₂ and O₂ in the solvent condition are uniformly discussed. Simulation of Grand Canonical Monte Carlo (GCMC) in MS 8.0 and calculations in Langmuir model reveal that Cu₂(µ₂-O₂CCH₃)₄ has good selectivity for CH₄ in natural gas (CH₄/CO₂/N₂) and SO₂ in fog (SO₂/NO/NO₂/H₂O/O₂), which would exhibit potential environmentally friendly applications.     

Ionic liquid gating control of magnetic anisotropy in Ni0.81Fe0.19 thin films

Voltage control magnetism is one of the most energy efficient pathway towards magnetoelectric (ME) device. Ionic liquid gating (ILG) method has already shown impressive manipulation power at the IL/electrode interface to influence the structure, orbital as well as spin of the electrode materials. As key material in anisotropy magnetoresistance sensor and spin valve heterostructure, the permalloy Ni_0.81Fe_0.19 was utilized as the electrode to investigate the ILG induced magnetic anisotropy change. In this work, we realized magnetic anisotropy control in Au/[DEME]⁺[TFSI]^-/Ni_0.81Fe_0.19 (2.5 nm)/Ta heterostructure via ILG caused electrostatic doping. This is evidenced in situ reversible ferromagnetic field (H_r) shift with electron spin resonance (ESR) spectrometer. Aiming at the question whether the charge accumulation at the ionic liquid interface is the main control mechanism at low voltage, we carefully tested the relationship between the change of resonance field and the amount of surface charge. It was found that these two had a good linear relationship between −1 V and +1 V. Defining the linear parameter as A whose value is 28.7 mT m²/Col. Unlike previously reported chemical regulation of Co, this article used ionic liquids to physically regulate NiFe, which has not been studied in the previous ionic liquid regulation. And NiFe has a narrower resonance line width for easy reference to microwave devices. In addition, It also has a stronger ferromagnetic signal than Co, which can be more easily detected as a sensor device. Therefore, this system is more promising. The ILG control NiFe may lead to a new kind of magnetoelectric sensor devices and path a new way to low energy consumption spintronics.     

On-chip multiphoton Greenberger–Horne–Zeilinger state based on integrated frequency combs

One of the most important multipartite entangled states, Greenberger–Horne–Zeilinger state (GHZ), serves as a fundamental resource for quantum foundation test, quantum communication and quantum computation. To increase the number of entangled particles, significant experimental efforts should been invested due to the complexity of optical setup and the difficulty in maintaining the coherence condition for high-fidelity GHZ state. Here, we propose an ultra-integrated scalable on-chip GHZ state generation scheme based on frequency combs. By designing several microrings pumped by different lasers, multiple partially overlapped quantum frequency combs are generated to supply as the basis for on-chip polarization-encoded GHZ state with each qubit occupying a certain spectral mode. Both even and odd numbers of GHZ states can be engineered with constant small number of integrated components and easily scaled up on the same chip by only adjusting one of the pump wavelengths. In addition, we give the on-chip design of projection measurement for characterizing GHZ states and show the reconfigurability of the state. Our proposal is rather simple and feasible within the existing fabrication technologies and we believe it will boost the development of multiphoton technologies.     

柱面微通道板的制备及其性能研究

针对未来空间天文学应用的超分辨率光谱成像仪器的需求，对低噪声柱面微通道板（MCP）的制备方法及其性能进行了研究. 提出了一种将光学抛光与热成型相结合的新的柱面MCP制备方法，利用不含放射性元素的低噪声MCP玻璃，制备出曲率半径为400mm、尺寸为30mm′46mm、长径比为80:1、通道直径12.5mm、通道间距15mm的柱面MCP，并将其与感应电荷楔条形阳极（WSA）组成光子计数探测器，对其暗计数率、分辨率进行了检测，暗计数率约为0.1counts/cm2×s.     

基于平面度的燃料电池电化学性能模拟

 固体氧化物燃料电池的翘曲会影响电极-盖板界面的接触情况，从而影响电化学性能，对相关制造工艺提出了很大的挑战．为了分析燃料电池平面度对放电过程的影响，揭示其潜在的风险，我们建立了两个基于有限元法的仿真模型，对考虑平面度缺陷的燃料电池封装和放电进行分析．在对固体氧化物燃料电池进行平面度测量的基础上，首先建立了具有真实燃料电池翘曲特性的几何模型，分析封装过程中接触压力的分布情况．然后将接触电阻的仿真结果导入到三维多物理场耦合模型中，模拟具有平面度缺陷的燃料电池电化学性能．计算结果展示了燃料电池两侧封装过程中接触压力的分布情况．通过对比有接触电阻和无接触电阻的燃料电池电流密度，分析了电池与盖板的接触对放电过程的影响．结果表明，燃料电池的凹陷面较难达到满意的接触状态，需要比凸起面更大的封装压力．燃料电池表面接触电阻的变化将引起电流传导路径的变化，产生局部高电流或低电流．这项工作强调了在燃料电池中保持均匀分布的接触电阻的重要性，为今后的优化工作奠定了基础．