A new catalyst based on a nickel(II) complex of diiminodiphosphine for hydrogen evolution and oxidation

Based on that hydrogen energy is widely used in fuel cells, we focus our interests on the design and research of new complexes that catalyze the reaction in both directions, such as hydrogen evolution reactions (HERs) and hydrogen oxidation reactions (HORs). A highly efficient catalyst for both hydrogen evolution and oxidation, based on a nickel(II) complex, [Ni-en-P₂](ClO₄)₂, has been designed and provided by the reaction of Ni(ClO₄)₂ with N,N′-bis[o-(diphenylphosphino)benzylidene]ethylenediamine (en-P₂) in our group. Its structure has been determined by X-ray diffraction. [Ni-en-P₂](ClO₄)₂ can electro-catalyze hydrogen evolution both from acetic acid and a neutral buffer (pH 7.0) with a turnover frequency (TOF) of 204 and 1327 mol of hydrogen per mole of catalyst per hour (H₂/mol catalyst/h) under an overpotential (OP) of 914.6 mV and 836.6 mV, respectively. [Ni-en-P₂](ClO₄)₂ also can electro-catalyze hydrogen oxidation with a TOF of 111.7 s⁻¹ under an OP of 330 mV. The results can be attributed to that [Ni^II-en-P₂](ClO₄)₂ has three good reversible redox waves at 1.01 (Ni^III/II), −0.79 (Ni^II/I) and −1.38 V (Ni^I/0) versus Fc^+/0, respectively. We hope these findings can afford a new method for the design of electrocatalysts for both H₂ evolution and H₂ oxidation.     

3D pore-interconnected calcium phosphate bone blocks for bone tissue engineering

Pore size and connectivity of artificial bone scaffolds play key role in regulating cell ingrowth and vascularization during healing. The objective of this study was to develop a novel process for preparing 3D pore-interconnected open-cell bone substitutes with varying pore sizes. This was achieved by thermal-induced expansion, drying, then sintering the mixture of biphasic calcium phosphate (BCP) and a thermal responsive porogen comprising chitosan (CS) and hydroxypropyl methyl cellulose (HPMC). The interpolymer complexes (IPCs) of CS/HPMC were prepared and investigated by FT-IR. The mixtures of IPCs/BCP were heated up to 100 °C for analyzing their thermal expansion properties. This resulted in ~13% and ~42% volume increment for IPC-1/BCP and IPC-2/BCP, respectively, while ~230% volume increased in the case of IPC-3/BCP (therefore chosen for sintering bone blocks). Heating rate-dependent (0.20–0.25 °C/min range) sintering profiles for IPC-3/BCP were utilized to produce BCP bone blocks. Gasification of IPC during sintering resulted in the formation of interconnected porous structures, and the morphology was investigated by SEM, revealing varying sizes ranging from 106 ± 13 μm to 1123 ± 75 μm. The pore size range of bone blocks from 235 ± 46 μm to 459 ± 76 μm portrayed significantly high MC3T3-E1 cell viability with prominent filopodial extensions, and elongated cells, depicting efficient biocompatibility. Therefore, the process for preparing porous interconnected 3D bone blocks were feasible, thereby serving as an alternative for potential bone tissue engineering applications.     

铜基化合物的可见光催化研究进展

与传统贵金属光催化剂相比，铜基光催化剂具有价格低廉、绿色环保、反应条件温和、光催化活性可调节等优势，受到合成化学家们广泛关注。本文简述了铜基催化剂的光催化历史，回顾了近五年来铜基化合物在可见光催化领域的研究成果与进展，总结了铜基催化剂的独立光催化机理与协同光催化机理；简要阐述了铜催化剂在不同类型反应中的应用，重点讨论了铜(Ⅰ)催化剂在烯烃官能化、碳-碳偶联、碳-杂偶联、原位催化等反应中的应用研究，表明铜基化合物在光催化合成领域具有很大的应用潜力。对未来的研究工作进行了展望，指出拓展催化剂的反应适用性、探索催化剂的氧化还原能力、进一步开发催化剂在手性合成中的应用将是该领域的研究重点。     

Electrocatalytic Reduction of CO2 to Ethylene by Molecular Cu‐Complex Immobilized on Graphitized Mesoporous Carbon

The electrochemical reduction of carbon dioxide (CO₂) to hydrocarbons is a challenging task because of the issues in controlling the efficiency and selectivity of the products. Among the various transition metals, copper has attracted attention as it yields more reduced and C2 products even while using mononuclear copper center as catalysts. In addition, it is found that reversible formation of copper nanoparticle acts as the real catalytically active site for the conversion of CO₂ to reduced products. Here, it is demonstrated that the dinuclear molecular copper complex immobilized over graphitized mesoporous carbon can act as catalysts for the conversion of CO₂ to hydrocarbons (methane and ethylene) up to 60%. Interestingly, high selectivity toward C2 product (40% faradaic efficiency) is achieved by a molecular complex based hybrid material from CO₂ in 0.1 m KCl. In addition, the role of local pH, porous structure, and carbon support in limiting the mass transport to achieve the highly reduced products is demonstrated. Although the spectroscopic analysis of the catalysts exhibits molecular nature of the complex after 2 h bulk electrolysis, morphological study reveals that the newly generated copper cluster is the real active site during the catalytic reactions.     

一种大型复杂构件加工新模式及新装备探讨

大型复杂构件是航空航天、能源、船舶等领域装备的核心结构件，此类构件通常具有尺寸大、形状复杂、刚性弱等特点。传统“分体离线加工-在线检测”模式存在工艺不稳定、过程复杂、柔性差、周期长等问题，以龙门式多轴数控机床加工为代表的“包容式”加工模式，难以适应大型复杂构件的高效高质量加工制造需求。提出一种基于移动式和吸附式机器人的多机协同原位加工新模式，通过多机器人系统自主寻位、精确定位加工与加工质量原位检测，实现大型复杂构件多安装面并行铣削、制孔与打磨等作业。多机器人系统包括移动式混联机器人、吸附式并联机器人、移动式串联铣削机器人、移动式双臂加工机器人和移动式打磨机器人。构建多机协同原位加工模式，需要揭示多机器人协同原位加工行为与大型弱刚性结构件质量控制的交互机理，面临着本体、测量、工艺和集成四个方面的挑战，需要设计高灵活、高刚度的移动式和吸附式加工机器人，解决移动机器人自主准确寻位和超大结构件原位高精检测难题，攻克加工变形误差在线补偿和振动抑制技术，通过集成实现多机协同高效高精加工，为大型复杂构件的高效高质量制造提供创新技术及装备，并实现此类构件制造核心技术及装备自主可控。     

基于对比折射法的三维静校正技术及其应用

在地形起伏剧烈、速度和厚度横向变化大的地区，折射静校正技术的应用受到诸多限制，主要表现在不能准确地识别和拾取来自于地下连续地质界面的折射波，使得精确求取的长波长静校正量困难。为此，提出了一种基于对比折射法的三维静校正技术。介绍了这种静校正技术的方法原理和特点，基于对比折射法的折射波至拾取实质上是一个折射层的对比分析解释过程，因此能准确地拾取折射波至，精确地求解低速带的绝对延迟时；然后利用延迟时和近地表速度模型（等效，时深，空变）反演表层模型，最终一次性完成基准面静校正（包含低速带校正和高程校正）。在黄土塬、沙漠以及沙漠和山地的接合部等地区，利用基于对比折射法的三维静校正技术进行静校正处理，使资料的品质得到了明显改善，反射同相轴连续性好，信噪比和分辨率高，构造形态清晰可靠，提高了勘探精度。     

环糊精降低重整汽油的苯含量

选用β环糊精（β-CD）和羟丙基-β环糊精（HP-β-CD）的水溶液分离混合烃中的苯，通过比较得出HP-β-CD对苯的分离具有较高的选择性。在重整原料油中采用HP-β-CD实现液-液分离，运用正交实验设计方法设计实验，得出最佳分离条件为：HP-β-CD溶液的含量30％，HP-β-CD溶液与重整汽油的体积比3：1，萃取次数9。在此工艺条件下，萃取后重整汽油中的苯含量从5．72％降到1．08％。     

双膦胺镍-甲基铝氧烷体系催化苯乙烯聚合

研究了具有新型结构的双膦胺镍配合物N,N-双(二苯膦基)-对甲氧基苯胺二氯化镍-甲基铝氧烷(PNP-N i-MAO)催化体系对苯乙烯聚合的催化性能,考察了聚合温度、n(A l)∶n(PNP-N i)、PNP-N i的浓度和苯乙烯的浓度对催化活性、苯乙烯转化率、聚苯乙烯相对分子质量及其分布的影响,并用核磁共振和凝胶色谱对聚苯乙烯的结构进行了表征。实验结果表明,在聚合温度25℃、聚合时间1h、n(A l)∶n(PNP-N i)=300、c(苯乙烯)=2.3m ol/L、c(PNP-N i)=0.4mm ol/L、甲苯为溶剂的适宜条件下,苯乙烯的转化率可达95%以上,催化活性达到5×105g/(m ol.h)左右。核磁共振和凝胶色谱表征结果显示,所得聚苯乙烯为无规结构,重均相对分子质量约为1×104,相对分子质量分布Mw/Mn约为2。     

Cu基络合物催化甲醇液相氧化羰化反应

针对甲醇液相氧化羰基化法合成碳酸二甲酯(DMC)工艺,开发了新型Cu基络合催化剂(CuB rnLm)。对CuB rnLm催化剂的活性及其稳定性进行了研究。实验结果表明,采用该催化剂,甲醇转化率和DMC选择性较高;元素价态和物质结构分析表明,CuB rnLm催化剂循环使用5次后仍保持较好的稳定性。采用正交设计和中心响应曲面法设计实验,并使用S tatistica软件进行统计分析,寻求出反应的主要影响因素,并得到优化的工艺条件:反应温度100~110℃、反应压力3.0~3.5M Pa、反应时间4~6h、CuB rnLm催化剂质量浓度(以甲醇的体积计)0.15~0.20g/mL。在此工艺条件下,甲醇转化率可达23%以上,DMC的选择性为96%~98%。     

Poly(vinyl pyrrolidone)—C70 complexes in aqueous solutions

Aqueous solutions of poly(vinyl pyrrolidone)-fullerene complexes (PVP-C₇₀) have been studied using static and dynamic light scattering methods. Two diffusive processes were detected. The slow diffusion was interpreted as dynamics of large intermolecular PVP-C₇₀ complexes while the fast diffusion was associated with the presence of individual PVP molecules in solution. It was also shown that the molecular weights and dimensions of PVP-C₇₀ complexes are smaller than for PVP-C₆₀ by a factor of 2.5-3. In aqueous solutions of PVP-C₇₀ complex the depolarization and dissymmetry of scattered light were observed in contrast to PVP-C₆₀ solutions. It reveals the existence of anisotropic structures in PVP-C₇₀ solutions. Intermolecular interactions within PVP-C₇₀ complexes are weak and a hydrodynamic field can destroy complexes.