Carbohydrate-based nanostructured catalysts: applications in organic transformations

The requirement of green and sustainable materials to prepare heterogeneous catalysts has intensified for practical reasons over the past few decades. Carbohydrates are possibly the most plentiful and renewable organic materials in nature with inimitable physiochemical properties, plausible low-cost and large-scale production, and sustainability features could be exploited in the generation of nanostructured heterogeneous catalysts. This review article outlines the organic transformations catalyzed by diverse carbohydrate-based nanostructured catalysts in greener and environmentally friendly processes. Selected examples are highlighted for a variety of organic reactions exploiting the proposed catalysts’ reactivity and reusability, and interactions with the intrinsic nature of the applied carbohydrate supports; advantages and speculated challenges of the introduced catalysts are deliberated as well.     

Current trends in the description of lanthanum strontium manganite oxygen electrode reaction mechanism in a high-temperature solid oxide cell

This review summarizes recent progress in understanding the oxygen reduction and evolution reactions at the lanthanum strontium manganite electrode of a high-temperature solid oxide cell. Information provided here is put into the perspective of the defect chemistry of lanthanum strontium manganite and its impact on the electrode reaction mechanisms itself. After summarizing recent views on the oxygen reduction reaction mechanism, the focus turns to the oxygen evolution reaction, which is significantly less treated in the literature. A combination of the information in the literature on both reactions was the basis for modified reaction mechanism of the oxygen evolution reaction to be proposed under consideration of recent experimental observations and theoretical findings.     

Analysis on First-stage Ignition of n-Heptane at Low Temperatures with a Lumped Skeletal Mechanism

Two-stage ignition exists in the low-temperature combustion process of n-heptane and the first-stage ignition also shows a negative temperature coefficient(NTC) phenomenon. To study key reactions and understand chemical principles affecting the first-stage ignition of n-heptane, a lumped skeletal mechanism with 62 species is obtained based on the detailed NUIGMech1.0 mechanism using the directed relation graph method assisted by sensitivity analysis and isomer lumping. The lumped mechanism shows good performance on ignition delay time under wide conditions. The study revealed that the temperature after the first-stage ignition is higher and a larger amount of fuel is consumed at lower initial temperatures. The temperature at the first-stage ignition is relatively insensitive to the initial temperature. Further sensitivity analysis and reaction path analysis carried out based on the lumped mechanism show that the decomposition of RO₂ to produce alkene and HO₂is the most important reaction to inhibit the first-stage ignitions. The chain branching explosion closely related to the first-stage ignition will be terminated when the rate constant for the RO₂ decomposition is larger than that of the isomerization of RO₂ to produce QOOH. The NTC behavior as well as other characteristics of the first-stage ignition can be rationalized from the competition between these two reactions.     

射频等离子制备石墨烯负载Co3O4催化剂及其析氧性能研究

氢能的引入能有效提升配电网的供电可靠性,而电解水制氢是实现低碳转型的关键技术,开发高效的电解水催化剂势在必行。过渡金属氧化物储量大、催化活性高,是具有广阔应用前景的析氧反应催化剂。本文通过射频等离子体处理制备石墨烯上负载Co₃O₄析氧催化剂,XRD、Raman和XPS测试结果显示,二维结构石墨烯的引入加速表面电子迁移,增大了反应面积。等离子体处理促进了纳米粒子在石墨烯上的负载,利用等离子体刻蚀作用在催化剂表面制造出大量碳结构缺陷和氧空位结构,改善了活性位点分布,有效调控Co₃O₄电子结构,提高析氧催化活性。电化学测试表明,本文中合成的Co₃O₄@rGO在电流密度为50 mA·cm^-2时的过电位为410 mV,动力学反应速率较快,表现出优于商业IrO₂的析氧催化活性。     

环加成反应、环合反应、电环化反应与环化反应的区别*

环加成反应、环合反应、电环化反应与环化反应都是合成有机环状化合物的成环反应,它们描述的反应类型完全不同。但是,它们却经常被误用或者混用。阐述了这4类反应的区别,希望能够从教学上明确这4类反应,从源头为将来的有机化学工作者建立起准确的概念。     

Nickel (II) tetrapyridyl complexes as electrocatalysts and precatalysts for water oxidation

Two nickel complexes, [Ni(tpen)](ClO₄)₂.0.5CH₃COCH₃ ( 1 ) and [Ni(tpbn)](ClO₄)₂ ( 2 ), of tetrapyridyl ligands N,N,N′,N′-tetrakis(2-pyridyl-methyl)-1,2-ethanediamine (tpen) and N,N,N′,N′-tetrakis(2-pyridyl-methyl)-1,4-butanediamine (tpbn) were prepared and their catalysis for water oxidation reaction (WOR) studied. In 0.1 M phosphate buffer solution (PBS) of pH 8.0, complex 1 is a homogeneous molecular catalyst with an overpotential of ~440 mV and a Faradaic efficiency of 89%. At pH ≥ 9.0, complex 1 degraded gradually during the catalytic process and formed NiO_x composite (nickel oxide with general formula Ni_xO_yH_z) active for WOR. In contrast, complex 2 deteriorated under measured conditions (pH 8.0–12.0) and formed NiO_x composite active for WOR. The NiO_x composite derived from 1 in 0.1 M PBS at pH 11.0 showed an activity with an overpotential of ~500 mV, a Tafel slope of ~90 mV/decade and a Faradaic efficiency of 97%. Mechanisms were proposed for water oxidation catalyzed by 1 and 2 . This work revealed that the catalytic activity of the nickel complexes was related to the flexibility of the tetrapyridyl ligands and the adaptability of the coordination sphere of the nickel(II) center.     

Copper-based metal–organic framework decorated by CuO hair-like nanostructures: Electrocatalyst for oxygen evolution reaction

We report a Cu-based metal–organic framework (MOF) decorated by CuO nanostructures as an efficient catalyst for the oxygen evolution reaction (OER). MIL-53(Cu) was synthesized by a hydrothermal approach using 1,4-bezenedicarboxylic acid as organic precursor and further annealed at 300°C to form CuO nanostructures on its surface. The produced electrocatalyst, CuO@MIL-53(Cu), was characterized using various techniques. Under alkaline conditions, the developed electrocatalyst exhibited an overpotential of 801 and 336 mV versus RHE at 10 and 1 mA cm⁻², respectively. The reproducibility of the catalytic performance was validated using several electrodes. It was confirmed that the CuO hair-like nanostructures grown on MIL-53(Cu) using thermal treatment exhibit high OER activity, good kinetics and durability. CuO@MIL-53(Cu) is an economic noble-metal-free OER electrocatalyst. It has potential for application as anode material for sustainable energy technologies like batteries, fuel cells and water electrolysis.     

MWCNTs@NHBut/PTA: New efficient solid acid catalyst for solvent free synthesis of benzochromenopyrimidines

In this study, a novel and eco‐friendly synthesis of benzochromenopyrimidines catalyzed by phosphotugstic acid immobilized on aminated multiwalled carbon nanotubes (MWCNTs@NHBut/PTA) is reported. New solid acid catalyst was prepared through a simple process with good percentage of organo metallic groups and characterized with FTIR, TEM, SEM, EDX and TGA techniques. Reusable catalytic system provides a convenient, safe and green pathway to generate a variety of benzochromenopyrimidines under mild conditions.     

Facile synthesis of graft copolymers containing rigid poly(dialkyl fumarate) branches by macromonomer method

Graft copolymers show microphase separated structure as seen in block copolymers and have lower intrinsic viscosity than block copolymers because of a branching structure. Therefore, considering molding processability, especially for polymers containing rigid segments, graft copolymers are useful architectures. In this work, graft copolymers containing rigid poly(diisopropyl fumarate) (PDiPF) branches were synthesized by full free‐radical polymerization process. First, synthesis of PDiPF macromonomers by addition‐fragmentation chain transfer (AFCT) was investigated. 2,2‐Dimethyl‐4‐methylene‐pentanedioic acid dimethyl ester was found to be an efficient AFCT agent for diisopropyl fumarate (DiPF) polymerization because of the suppression of undesired primary radical termination, which significantly took place when common AFCT agent, methyl 2‐(bromomethyl)acrylate, was used. Copolymerization of PDiPF macromonomer with ethyl acrylate accomplished the generation of the graft copolymer having flexible poly(ethyl acrylate) backbone and rigid PDiPF branches. The graft copolymer showed a microphase separated structure, high transparency, and characteristic thermal properties to PDiPF and poly(ethyl acrylate). © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2474–2480