Ruthenium-Catalyzed Direct Asymmetric Reductive Amination of Diaryl and Sterically Hindered Ketones with Ammonium Salts and H2

A Ru-catalyzed direct asymmetric reductive amination of ortho-OH-substituted diaryl and sterically hindered ketones with ammonium salts is reported. This method represents a straightforward route toward the synthesis of synthetically useful chiral primary diarylmethylamines and sterically hindered benzylamines (up to 97 % yield, 93–>99 % ee). Elaborations of the chiral amine products into bioactive compounds and a chiral ligand were demonstrated through manipulation of the removable and convertible -OH group.     

“Self-Lockable” Liquid Crystalline Diels–Alder Dynamic Network Actuators with Room Temperature Programmability and Solution Reprocessability

Novel main-chain liquid crystalline Diels—Alder dynamic networks (LCDANs) were prepared that exhibit unprecedented ease for actuator programming and reprocessing compared to existing liquid crystalline network (LCN) systems. Following cooling from 125 °C, LCDANs are deformed with aligned mesogens self-locked at room temperature by slowly formed Diels–Alder (DA) bonds, which allows for the formation of solid 3D actuators capable of reversible shape change, and strip walker and wheel-capable light-driven locomotion upon either thermally or optically induced order–disorder phase transition. Any actuator can readily be erased at 125 °C and reprogrammed into a new one under ambient conditions. Moreover, LCDANs can be processed directly from melt (for example, fiber drawing) and from solution (for example, casting tubular actuators), which cannot be achieved with LCNs using exchangeable covalent bonds. The combined attributes of LCDANs offer significant progress toward developing easily programmable/processable LCN actuators.     

具有优异甲醇耐受性的Rh掺杂PdCu有序金属间化合物纳米粒子增强氧还原电催化

Direct methanol fuel cells (DMFCs), as one of the important energy conversion devices, are of great interest in the fields of energy, catalysis and materials. However, the application of DMFCs is presently challenged because of the limited activity and durability of cathode catalysts as well as the poisoning issues caused by methanol permeation to the cathode during operation. Herein, we report a new class of Rh-doped PdCu nanoparticles (NPs) with ordered intermetallic structure for enhancing the activity and durability of the cathode for oxygen reduction reaction (ORR) and achieving superior methanol tolerance. The disordered Rh-doped PdCu NPs can be prepared via a simple wet-chemical method, followed by annealing to convert it to ordered phases. The results of transmission electron microscopy (TEM), scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), power X-ray diffraction (PXRD) analysis and high resolution TEM (HRTEM) successfully demonstrate the formation of near-spherical NPs with an average size of 6.5 ± 0.5 nm and the conversion of the phase structure. The complete phase transition temperatures of Rh-doped PdCu NPs and PdCu are 500 and 400 ℃, respectively. The molar ratio of Rh/Pd/Cu in the as-synthesized Rh-doped PdCu NPs is 5/48/47. Benefitting from Rh doping and the presence of the ordered intermetallic structure, the Rh-doped PdCu intermetallic electrocatalyst achieves the maximum ORR mass activity of 0.96 A·mg^-1 at 0.9 V versus reversible hydrogen electrode (RHE) under alkaline conditions—a 7.4-fold enhancement compared to the commercial Pt/C catalyst. For different electrocatalysts, the ORR activities follow the sequence, ordered Rh-doped PdCu intermetallics > ordered PdCu intermetallics > disordered Rh-doped PdCu NPs > disordered PdCu NPs > commercial Pt/C catalyst. In addition, the distinct structure endows the Rh-doped PdCu intermetallics with highly stable ORR durability with unaltered half-wave potential (E_1/2) and mass activity after continuous 20000 cycles, which are higher than those of other electrocatalysts. Furthermore, the E_1/2 of the Rh-doped PdCu intermetallics decreases by only 5 mV after adding 0.5 mol·L^-1 methanol to the electrolyte, while the commercial Pt/C catalyst negatively shifts by 235 mV and a distinct oxidation peak can be observed. The results indicate that the ORR activity of the Rh-doped PdCu intermetallic electrocatalyst can be well maintained even in the presence of poisoning environment. Our results have demonstrated that Rh-doped PdCu NPs with ordered intermetallic structures is a potential electrocatalyst toward the next-generation high-performance DMFCs.     

高碳铬铁在氢氧化钠水溶液中电化学氧化过程

铬铁电化学氧化法是一种新的制备铬酸钠的方法,然而高碳铬铁在NaOH水溶液中的电化学氧化过程尚不明确。 采用循环伏安法(CV)、稳态极化法(LSV)等电化学测试方法对金属铬、高碳铬铁在NaOH水溶液中的电化学氧化过程进行研究,通过扫描电子显微镜(SEM)、能量散射谱(EDS)和X射线光电子能谱(XPS)对高碳铬铁电解后固相产物表征,判断固相产物的组成。 结果表明,高碳铬铁不同于金属铬的电氧化过程,它在NaOH溶液中通过Cr(0)→Cr(Ⅵ)的电氧化方式生成铬酸钠,中间产物Cr(OH)₃和Fe(0)发生电化学反应生成稳定的FeCr₂O₄。 随着NaOH浓度的增加,电势较低时,受高碳铬铁中Fe(0)的影响,高碳铬铁容易在NaOH水溶液中发生钝化;当电势足够正时,钝化膜溶解,生成铬酸钠、氢氧化铁和亚铬酸亚铁,同时,阳极表面有氧气析出。 高碳铬铁电化学氧化制备铬酸钠的适宜条件:碱浓度≥2 mol/L,阳极电势≥1.6 V(vs.SCE)。     

光电催化二氧化碳还原研究进展

CO_2是最常见的化合物,作为潜在的碳一资源,可用于制备多种高附加值的化学品,如一氧化碳、甲烷、甲醇、甲酸等。传统的热催化转化CO_2方法能耗高,反应条件苛刻。因此,如何在温和条件下高效地将CO_2转化成高附加值的化学品,一直以来是催化领域的研究热点和难点之一。光催化技术反应条件温和、绿色环保。然而,纯光催化反应普遍存在太阳能利用效率有限,光生载流子分离效率低等问题。针对上述问题,在光催化的基础上引入电催化,可以提高载流子的分离效率,在较低的过电位下,实现多电子、质子向CO_2转移,从而提高催化反应效率。总之,光电催化技术可以结合光催化和电催化的优势,提高CO_2催化还原反应效率,为清洁、绿色利用CO_2提供了一种新方法。本文依据光电催化CO_2还原反应基本过程,从光吸收、载流子分离和界面反应等三个角度综述了光电催化反应的基本强化策略,并对未来可能的研究方向进行了展望。     

可持续高分子-纤维素新材料研究进展

21世纪"绿色"化学已成为世界各国社会经济发展中的研究与开发战略方向.纤维素是自然界中储量最丰富的天然高分子,是重要的可再生资源以及未来的主要工业原料.然而由于纤维素存在着大量的分子内以及分子间氢键,其结构致密,难以溶解或熔融进一步加工.本文简要介绍了近几年来关于直接使用物理溶剂方法(非衍生化)对纤维素材料开发利用的新进展,主要包括以下4个方面:(1)纤维素在"绿色"溶剂-碱/尿素以及离子液体体系中的溶解和再生;(2)纳米纤维素的制备以及组装;(3)木材纳米技术的开发及利用;(4)细菌纤维素基材料等,旨在推进"绿色"技术实现纤维素资源的研究开发及利用.     

利用自由基引发的1,2-炔基迁移实现非活性烯烃的炔膦酰化

研究了1,4-烯炔衍生物与二芳基膦氧化物在银介导下发生的炔酰化反应.该反应利用自由基引发的1,2-炔基迁移策略合成了一系列γ-酮膦氧化物,产率适中.该反应机理可能涉及膦中心自由基与乙烯基的加成、3-exo-dig环化和1,2-炔基迁移等连续的过程,一步形成了C-P、C-C键等化学键,实现了非活性烯烃的双官能化.     

NN型双齿半夹心Ru(Ⅱ)化合物:无受体脱氢环化合成喹啉和吡咯衍生物的催化剂

四个含NN型双齿配体的半夹心(η^6-p-cymene)Ru(II)化合物被成功制备.这四个化合物分别为(η^6-p-cymene)-Ru(C5H4N-C5H3N-OH)(1),(η^6-p-cymene)Ru(C5H4N-CH2-C5H4N)(2),(η^6-p-cymene)Ru(C5H4N-CH2-C5H3N-OH)(3)和(η^6-p-cymene)Ru(C5H4N-CH2-C5H3N-OCH3)(4).这些化合物通过核磁氢谱、碳谱和元素分析等手段表征,化合物2的结构被X射线单晶衍射证实.将这些化合物应用于催化氨醇与酮的环化反应,其中3的催化效率最高.在0.5mol%化合物3的存在下,制备了一系列喹啉和吡啶衍生物.     

UV-light irradiation preparation of soybean residue-based hydrogel composite from inorganic/organic hybrids for degradable slow-release N-fertilizer

Research on Chemical Intermediates - Biomass waste, which was the by-product generated along with the production of food, was transformed into high-value constituent in slow-release fertilizers....     

Recent advances in metal-organic frameworks for lithium metal anode protection

The lithium metal battery has been considered as a promising candidate for next generation batteries.However,safety concerns caused by uncontrollable lithium dendrite growth on lithium anode are severely hampering the commercial application.Metal-organic frameworks(MOFs)become one of the most attractive materials due to the high porosity,structural designability and tunability.With unique open channels and pores as well as functional components in MOFs,the transportation and deposition of lithium ions can be regulated,which leads to enhanced electrochemical prope rties.Various strategies for lithium metal protection are proposed in recent wo rks on applications of MOFs in lithium metal batteries.In this review,we highlight latest key approaches in this field and discuss the prospects for MOFs in advanced Li anodes.