Pt/ZnO 在室温水相无碱条件下绿色催化苯甲醇选择性氧化

醇类化合物选择性氧化是有机合成中一个非常重要的反应, 在精细化工领域具有重要应用. 而以水为绿色溶剂, 分子氧为绿色氧化剂实现醇类化合物选择性氧化是绿色化学领域的一大挑战. Pt 催化剂由于其优异的活化氧气和 C-H 键的能力在该反应中得到了广泛应用. 但是, 常规的 Pt 催化剂通常需要在较高温度和较高氧气压力以及加碱的条件下才能发挥作用, 从而引起了催化剂腐蚀等一系列问题. 从绿色化学角度出发, 进一步优化 Pt 催化剂, 让其能够在室温无碱条件下以空气为氧化剂选择性氧化醇类合成羰基化合物具有重要的研究价值和应用前景.本文通过化学还原法制备了 Pt/ZnO 催化剂, 系统研究了该催化剂在水相无碱条件下选择性氧化苯甲醇生成苯甲醛反应中的催化性能. X 射线电子衍射和透射电镜等结果表明, Pt 颗粒较小(3.2 ± 0.3 nm), 均匀分散在 ZnO 载体上; X 射线光电子能谱表明 ZnO 载体能够稳定 Pt 纳米颗粒表面的 Pt0物种. 上述催化剂在水相苯甲醇选择性氧化反应中, 在室温下即可催化空气高选择性氧化苯甲醇到苯甲醛 (选择性>99%), 并表现出比 Pt/SiO2, Pt/Al2O3, Pt/TiO2, Pt/Ca(Mg)-ZSM-5 等催化剂更为优异的催化活性. 这可归结于 Pt 和 ZnO 之间的协同作用. 该协同作用通过动力学实验和密度泛函理论计算 (DFT)得到了证实. 氧分压实验表明, 在以空气为氧化剂时, O2的活化并不是限制 Pt/ZnO 催化活性的关键因素, 而动力学同位素效应实验则证实了苯甲醇的 C-H 键活化是整个反应的决速步骤. 通过构建不同的理论模型, 分别计算了 Pt/ZnO 界面处以及纯 Pt 位点上苯甲醇选择性氧化的反应过程. 结果表明, 苯甲醇和氧气分子倾向于分别在 ZnO 和 Pt 上进行吸附, 随后由吸附的氧气分子来活化苯甲醇中的 C-H 键, 进而生成苯甲醛和水. 而当 ZnO 不参与苯甲醇的吸附活化时, 整个反应的活化能会大大提高, 表明 ZnO 和 Pt 之间的协同作用对于整个反应至关重要. 此外, Pt/ZnO 表现出非常优异的稳定性, 循环使用 4 次后, 催化剂结构以及催化活性没有显著变化.进一步向 Pt/ZnO 催化剂中引入少量 Bi 元素对 Pt 的电子结构进行修饰, 可以将 Pt/ZnO 的催化活性提高 3 倍. 所制备的 Pt/Bi-ZnO 复合物是目前报道的相同条件下催化苯甲醇选择性氧化反应转化频率 (45.1 h-1)最高的催化剂.     

Anomalous europium luminescence in LaF3

Optical spectra (absorption, emission, excitation, decay) and dielectric relaxation were measured for divalent europium and partially for ytterbium in lanthanum fluoride crystals. Optical absorption of LaF₃–Eu²⁺ contains not only asymmetric weakly structured band at 245 nm but also less intense bands at 330, 380 nm. Broadband Eu²⁺ emission at 600 nm appeared below 80 K with decay time 2.2 μs at 7.5 K. Emission at 600 nm is attributed to so-called anomalous luminescence. Bulk conductivity is directly proportional to absorption coefficient of Eu²⁺ bands. Dielectric relaxation peak of LaF₃–EuF₃ is attributed to rotation of dipoles Eu²⁺-anion vacancy. The long-wavelength absorption at 300–400 nm region are assigned to transitions from 4f⁷Eu²⁺ ground state to states of neighbouring fluorine vacancy.     

珍稀特有植物华顶杜鹃的种群结构和种间联结

华顶杜鹃（Rhododendron huadingense）因分布地域的局限和资源量的稀少,被列为浙江省珍稀濒危植物。基于珍稀特有植物华顶杜鹃主要分布区的样地调查数据,通过分析群落相似性、种群结构,并基于2×2联列表,应用共同出现百分率PC、联结系数AC、Pearson积矩相关系数r_p和Spearman秩相关系数r_s等方法对华顶杜鹃乔木层22个主要物种、灌木层24个主要物种的种间联结的显著性和关联强度进行了定量测定,以揭示华顶杜鹃群落不同结构层次中主要物种的种间关系及其种群濒危的原因。结果显示：（1）华顶杜鹃生长在光照较强的阳坡,不同产地所处群落物种组成差异较大。（2）种群结构显示,各群落均处于不同程度的衰退阶段,幼苗和幼树储备不足,种群呈衰退趋势;各样地的龄级结构不完整,普遍出现断代现象。（3）方差比率VR和统计量W表明,华顶杜鹃群落中物种整体关联性不显著;PC值显示乔木层和灌木层共507个种对,有183个相互独立,其余大部分PC值小于0.6,联结性较弱;AC值显示,乔木层和灌木层中除25个种对具有显著的联结性外,其余AC值的绝对值小于0.6;r_p值和r_s值正负关联比在0.36~0.85,显著检验率在0.06~0.08。表明华顶杜鹃所在群落种间关系较为松散,整体关联性弱;大部分物种生态习性差异较大,在共存时无法达到资源的最佳分配和利用状态,群落尚处不稳定阶段。为抑制其种群的衰退趋势,应加强对华顶杜鹃个体和群落生境的保护,需要适当的人为干预。     

Quantum Interface between a Superconducting Qubit and Spin Ensembles

An experimentally feasible strong coupling system between a spin ensemble and a superconducting qubit is studied. The coupling strength can be exponentially enhanced by applying the squeezing transformations to the system. By means of the two spin ensembles commonly coupled to a superconducting qubit, a set of universal nonadiabatic holonomic single‐qubit quantum gates can be realized in a decoherence‐free subspace. Furthermore, this proposal is robust with respect to decay of the system parameters, and it is experimentally feasible with currently available technology.     

One-step implementation of a multi-target-qubit controlled phase gate with cat-state qubits in circuit QED

We propose a single-step implementation of a muti-target-qubit controlled phase gate with one catstate qubit (cqubit) simultaneously controlling n–1 target cqubits. The two logic states of a cqubit are represented by two orthogonal cat states of a single cavity mode. In this proposal, the gate is implemented with n microwave cavities coupled to a superconducting transmon qutrit. Because the qutrit remains in the ground state during the gate operation, decoherence caused due to the qutrit’s energy relaxation and dephasing is greatly suppressed. The gate implementation is quite simple because only a single-step operation is needed and neither classical pulse nor measurement is required. Numerical simulations demonstrate that high-fidelity realization of a controlled phase gate with one cqubit simultaneously controlling two target cqubits is feasible with present circuit QED technology. This proposal can be extended to a wide range of physical systems to realize the proposed gate, such as multiple microwave or optical cavities coupled to a natural or artificial three-level atom.     

凹槽状PDMS基底上水滴的挥发及Cassie-Wenzel转变行为

通过在线跟踪水滴在凹槽状聚二甲基硅氧烷(PDMS)基底上的挥发行为, 研究了蒸馏水的挥发规律Cassie-Wenzel转变行为. 结果表明, 初始阶段, 水滴处于Cassie状态, 且在垂直于凹槽方向(V)和平行于凹槽方向(P)上存在显著的各向异性. 水滴的挥发过程依次表现出接触直径不变模式、 接触角不变模式及共同减小模式, 与平滑基底上水滴的挥发规律类似. 在挥发过程中, 发生了Cassie-Wenzel转变, 转变发生的时间与PDMS基底上突起部分的面积分数(即固相率)呈现良好的线性关系. 随着挥发的进行, 水滴的各向异性在接触角不变模式阶段消失, 即挥发导致水滴从开始的椭球缺状变为球缺状.     

Modified phonon confinement model for size dependent Raman shift and linewidth of silicon nanocrystals

A modified phonon confinement model considering the size distribution, an improved phonon dispersion curve and a confinement function is developed for the calculation of size dependent Raman spectra of the silicon (Si) nanocrystals. The model is capable of simultaneous calculations of the Raman shift, intensity and linewidth. The calculated size dependent redshift and linewidth of Raman spectra are in good agreement with the available experimental data in literature and better than previously reported theoretical results. The rapid rise in the redshift and linewidth for relatively smaller Si nanocrystals are well reproduced. The asymmetric behavior of Raman spectra is also obtained from the present model.     

A TRILAYER DERMAL EQUIVALENT CONTAINING SILVER NANOPARTICLES WITH ENHANCED ANTIBACTERIAL PROPERTY

A dermal equivalent having a trilayered structure was designed by combining a silver nanoparticles incorporated chitosan film with a bilayer collagen-chitosan/silicon membrane dermal equivalent(BDE).The silver nanoparticles prepared at different conditions were characterized by UV-Vis and transmission electron microscopy(TEM).The macroscopic sharp and the microstructure of the trilayer dermal equivalent(TDE) were also studied.Then,the in vitro antibacterial property of TDE was evaluated by the antibacter...     

锂电池中低成本碳包覆磷酸铁锂正极材料的合成及其性能

磷酸铁锂作为动力锂离子电池的正极材料正逐渐走向市场.以Li3PO4,FePO4,Fe粉以及乙醇为原料,采用高温热分解方法成功地制得乙醇碳包覆的LiFePO4正极材料.实验结果表明,该LiFePO4/C材料颗粒均匀,分散性好,粒径大约在200nm～1μm之间,颗粒表面被碳包覆,颗粒之间由碳纤维连接.该正极材料首次放电容量达137mAh·g-1,首次充放电库仑效率在95%以上,50次循环后,放电容量基本不衰减,显示出良好的循环稳定性和可逆性.本研究降低了锂离子电池的生产成本,显示了良好的工业化应用前景.     

毛细管电泳氨类手性药物对映体拆分机理研究

手性药物及其对映体在药理上可表现出较大的差异,对它们进行研究将具有重要的理论意义和实用价值[1,2].毛细管区带电泳因其分离效率高、药品和试剂用量少、方法简单而成为目前手性拆分鉴定的重要方法之一[3].