Proton Intercalation/De-Intercalation Dynamics in Vanadium Oxides for Aqueous Aluminum Electrochemical Cells

Understanding cation (H⁺, Li⁺, Na⁺, Al³⁺, etc.) intercalation/de-intercalation chemistry in transition metal compounds is crucial for the design of cathode materials in aqueous electrochemical cells. Here we report that orthorhombic vanadium oxides (V₂O₅) supports highly reversible proton intercalation/de-intercalation reactions in aqueous media, enabling aluminum electrochemical cells with extended cycle life. Empirical analyses using vibrational and x-ray spectroscopy are complemented with theoretical analysis of the electrostatic potential to establish how and why protons intercalate in V₂O₅ in aqueous media. We show further that cathode coatings composed of cation selective membranes provide a straightforward method for enhancing cathode reversibility by preventing anion cross-over in aqueous electrolytes. Our work sheds light on the design of cation transport requirements for high-energy reversible cathodes in aqueous electrochemical cells.     

Crystallization-Induced Reversal from Dark to Bright Excited States for Construction of Solid-Emission-Tunable Squaraines

Squaraines (SQs) with tunable emission in the solid state is of great importance for various demands; however a remaining challenge is emission quenching upon aggregation. Herein, a unique SQ, named as CIEE-SQ, is designed to exhibit strong emission in crystal, undergoing crystallization-induced reverse from dark ¹(n+σ,π*) to bright ¹(π,π*) excited states. Such an excited state of CIEE-SQ can be subtly tuned by molecular conformation changes during the unexpected temperature-triggered single-crystal to single-crystal (SCSC) reversible transformation. Furthermore, co-crystallization between CIEE-SQ and chloroform largely stabilize the ¹(π,π*) state, enhancing the transition dipole moment and decreasing the reorganization energy to boost the fluorescence, which is promising in data encryption and decryption.     

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.     

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。     

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....     

叶丝在增温增湿与滚筒烘丝工序中香味组分变化分析

该文研究了制丝线增温增湿和滚筒烘丝工序加工对叶丝香味组分的影响,采用溶剂超声萃取前处理结合GC-MS法测定叶丝的香味组分,并对SIROX增温增湿工序和滚筒烘丝工序前后叶丝香味组分的相对含量进行了分析,比较了工序前后、工序间香味组分的变化趋势。结果显示:①经SIROX增温增湿工序加工后,乙酸、苯甲醇等18种组分相对含量减少,糠醇、2,4-二羟基-2,5-二甲基-3(2H)-呋喃-3-酮等6种组分相对含量增加;②经滚筒烘丝工序加工后,乙酸、麦芽酚等14种组分相对含量减少,糠醇、糠醛等6种组分相对含量增加;③经增温增湿及滚筒烘丝两工序后,乙酸、2,3-丁二醇等23种组分相对含量减少,糠醇、2,4-二羟基-2,5-二甲基-3(2H)-呋喃-3-酮等4种组分相对含量增加;④两工序间的温度、湿度剧烈变化,使叶丝内部组分发生了美拉德反应、降解反应、挥发等,香味组分经两个工序后发生了一系列显著变化。该研究对提升卷烟产品质量、优化工艺参数、开发高质量产品具有重要意义。     

Rational Synthesis of Amorphous Iron‐Nickel Phosphonates for Highly Efficient Photocatalytic Water Oxidation with Almost 100 % Yield

A simple solvent ligation effect was successfully used to disrupt the growth of a model compound, Fe[(OH)(O₃P(CH₂)₂CO₂H)]?H₂O (MIL‐37), into an extended 2D structure by replacing water with dimethylformamide (DMF) as the solvent during the synthesis. Owing to the lack of ?OH group, which provides the corner‐sharing (binding) oxygen atoms for the octahedra, an amorphous and porous structure is formed. When Fe³⁺ is partially replaced by Ni²⁺, the amorphous structure remains and the resultant binary metal catalyst displays excellent photocatalytic oxygen evolution activity with almost 100 % yield achieved under visible light irradiation using [Ru(bpy)₃]²⁺ as the photosensitizer. This study opens up new possibilities of using the simple solvent effect to synthesize high surface area metal phosphonates for catalytic and other applications.