The electrochemical production of Adiponitrile (ADN) is a critical step in the manufacture of Nylon 6,6. This study provides a thorough understanding of the factors affecting this process, leading to design guidelines that help maximize selectivity, ADN production rate, and energy productivity of the system.

Organic hydrogenations are key steps in the production of numerous valuable chemicals. Their requirement for high temperature, pressure, and compressed hydrogen has motivated the interest to develop safer electrocatalytic hydrogenation (ECH) routes in benign aqueous electrolytes. However, faradaic efficiencies in organic ECH tend to be greatly limited by competition with the hydrogen evolution reaction and low reactant solubility, which hinders the implementation of these more sustainable hydrogenation routes. Using the hydrogenation of adiponitrile to hexamethylenediamine (HMDA), a monomer used in the production of nylon-6,6, as a case study, we investigate the effect of reactant concentration, temperature, pH, and organic cosolvents on the ECH of nitrile groups with Raney nickel electrodes. Higher reactant concentrations, alkaline electrolytes, and mild temperature (40 °C) are key conditions that enhance the hydrogenation of organic substrates against hydrogen evolution. A maximum faradaic efficiency of 92% toward HMDA was obtained in aqueous electrolytes at −60 mA cm–2. The addition of an organic cosolvent is subsequently studied to evaluate the effect of enhanced reactant solubility, achieving a 95% faradaic efficiency at the same current density with 30% methanol by volume in water. The insights gained from this study are relevant for the design of energy efficient organic ECH and can help accelerate the implementation of sustainable chemical manufacturing.

Soft materials can sustain large, elastic, and reversible deformations, finding widespread use as elastomers and hydrogels. These materials constitute 3-D polymer networks and are typically synthesized by cross-linking polymer chains or copolymerizing monomer and cross-linker. Seminal investigations have enabled control over the network architecture by cross-linking chains of poly­(dimethylsiloxane), poly­(1,4-butadiene), or tetra-poly­(ethylene glycol); however, as soft materials become attractive for robotics, electronics, and prosthetics, codesigning the network architecture, mechanical, and functional properties has become pressing. We investigate the relationship among reaction pathway, network architecture, and mechanical properties in poly­(ethyl glycidyl ether) networks synthesized by epoxide ring-opening polymerization with two organoaluminum catalysts. The key result is that uncontrolled polymerizations yield loosely cross-linked, entangled, soft, and extensible networks, whereas more controlled polymerizations, instead, lead to highly cross-linked, stiff, and brittle networks. Such catalytic control over network architecture and mechanical properties could enable design of novel soft, tough, and functional materials.