Electrochemical milling and faceting: size reduction and catalytic activation of palladium nanoparticles

Improved performance through milling: A method for enhancing the catalytic activity of supported metal nanoparticles is reported. This method enhances the activity for the ethanol electro-oxidation of a supported palladium catalyst. The much higher catalytic performance is ascribed to the increased electrochemically active surface area as well as the generation of high-index facets at the milled nanoparticle surface.     

有机电化学合成简谈

本文简要介绍了有机电化学合成的体系,研究方法和技术及主要特征。以C=C类物质为例介绍了有机电化学合成中的各类反应,并以己二腈的电合成为例介绍了相应的工业化应用。试图以CO2的电化学固定利用为例介绍了有机电化学合成的研究动向。     

Ionic liquid analogues formed from hydrated metal salts

A dark green, viscous liquid can be formed by mixing choline chloride with chromium(III) chloride hexahydrate and the physical properties are characteristic of an ionic liquid. The eutectic composition is found to be 1:2 choline chloride/chromium chloride. The viscosity and conductivity are measured as a function of temperature and composition and explained in terms of the ion size and liquid void volume. The electrochemical response of the ionic liquid is also characterised and it is shown that chromium can be electrodeposited efficiently to yield a crack-free deposit. This approach could circumvent the use of chromic acid for chromium electroplating, which would be a major environmental benefit. This method of using hydrated metal salts to form ionic liquids is shown to be valid for a variety of other salt mixtures with choline chloride.     

Biomass-based green chemistry: sustainable solutions for modern economies

Abstract

Biomass and renewable raw materials are the basis and driver for an even greater alignment of industry to the principles of green chemistry and sustainability. Nature provides a remarkably wide range of renewable raw materials with varying properties and differing chemical compositions. Renewable raw materials are therefore especially interesting as alternatives to fossil resources for energy generation and as starting materials for industrial chemistry. Since various forms of biomass are also essential for human nutrition and animal feed, their use as feedstocks for other purposes must be balanced. Ideally, the biomass remaining after the nutritious components are removed can serve as a feedstock. Examples of applications that use biomass as starting materials include adhesives, textile and leather, cosmetics, cleaning agents, coatings, paints, printing inks, crop protection, lubricants and dietary supplements.     

Carbocatalysis: The State of “Metal‐Free” Catalysis

The rise in global demand for crucial chemical compounds has driven immense research in the fundamental science of catalysis. Graphene and its derivatives (chemically modified graphene, CMGs) have recently emerged as a new class of heterogeneous catalyst that promises economically viable and greener routes to these compounds. Although CMGs possess unique catalytic properties, the actual active sites are often points of discussion. Current minimal understanding on the possible effects of metallic impurities on the electrocatalytic performances of these CMGs calls forth the need to raise awareness on possible metallic impurities misrepresenting the actual chemical catalytic performances of the CMGs. This Minireview highlights the latest advances in the application of CMGs as catalysts, with an emphasis on the possible effects of metallic impurities on CMG catalysis.     

Electrochemistry in solids prepared by sol-gel processes

Sol-gel chemistry provides a route to preparing inorganic polymers with ionically conducting properties by room temperature synthetic routes. The products, which are rigid solids, are well-suited as media for conventional electrochemical techniques such as cyclic voltammetry. This property, when combined with their ability to host a wide variety of species, has allowed development of a variety of devices of interest in electrochemistry and analytical chemistry. Examples include cathodes for fuels cells, electrochromic devices, biosensors, and amperometric sensors for analytes in the gas phase. In this review, the emphasis will be on reported applications to analytical chemistry; however, studies on the general properties of these materials and on their use in electrochemical science also will be summarized because they may provide the basis for further development of sensors.     

A Green Synthesis of Nanosheet‐Constructed Pd Particles in an Ionic Liquid and Their Superior Electrocatalytic Performance

The ionic liquid 1‐ethyl‐3‐methylimidazolium acetate ([EMIM]Ac) is investigated as a solvent for the synthesis of Pd particles. Interestingly, nanosheet‐constructed Pd particles could be successfully synthesized in [EMIM]Ac without any additional reducing agent and template under ionothermal conditions. [EMIM]Ac itself works as the solvent, the reducing agent, and the template for the formation of these interesting Pd particles, making this method complementary to the well‐known ionic‐liquid‐precursor approach. Furthermore, [EMIM]Ac can be recycled with no loss of activity for the formation of nanosheet‐constructed Pd particles within our studied cycles. Specifically, the nanosheet‐constructed Pd particles exhibit superior electrocatalytic activity and stability towards ethanol oxidation and formic acid oxidation compared with commercially available Pd black catalyst, thus demonstrating their promising applications in fuel‐cell area. The current approach, thus, presents a green approach towards the synthesis of Pd particles, using only a simple palladium salt and an ionic liquid.     

Metal- and Additive-Free Electrochemical Oxidation of Benzylic C−X Bonds to Carbonyl Groups

A scalable electrochemical strategy for oxidation of various benzylic C−X bonds to carbonyl groups was achieved. The protocol runs under mild reaction conditions and air atmosphere in a simple undivided electrolysis cell, H₂O as oxygen source, and cheap graphite plates as both anode and cathode. In addition, the electrolysis strategy features good functional groups tolerance for selectively generating structure versatile ketones, aldehydes, and esters.