Electrochemical Synthesis Methods

While some are calling to “return to the flatland”… we went full 3D. 🚨 Just published in Royal Society of Chemistry #GreenChemistry 🔗 https://lnkd.in/eQiy_Sv2 Introducing eSpiro – a sustainable electrosynthetic method for building spiroketals via anodic oxidation of malonic acids. No metals. No mercury. No excuses. Developed at the University of Greenwich in collaboration with AstraZeneca, this work brings a greener, scalable, and flow-compatible alternative to the table—challenging conventional routes that rely on harsh reagents or transition metals. 🔹 Up to 98% yield in batch 🔹 Broad functional group tolerance 🔹 Preliminary flow setup success 🔹 Practical, electro-mediated spirocyclisation from cheap malonates Congrats to Marylise Triacca, Carl Reens & Hamish Stephen for pushing the boundaries — or rather, bending them into a spiro! #GreenChemistry #Electrosynthesis #eSpiro #Spiroketals #SustainableSynthesis #FlowChemistry #FlatlandDebate #OrganicChemistry #AstraZeneca #UniversityOfGreenwich #RSC Greenwich Research and Innovation

Metal–nitride–mediated electrochemical #ammonia synthesis has emerged as a promising alternative to the Haber–Bosch process, offering the potential for decentralized, low-carbon fertilizer production powered by renewable electricity. In this context, calcium-nitride–mediated ammonia synthesis stands out as an attractive pathway because of calcium’s strong nitrogen affinity and favorable reaction thermodynamics. But despite its promise, practical implementation has been limited by persistent challenges—most notably the instability of calcium nitride intermediates, poor gas–liquid interface management, and slow HOR kinetics in non-aqueous electrolytes. Our latest study ( https://lnkd.in/g6QQwb-Y ) delivers several critical insights that address these bottlenecks head-on. We show that stabilizing Ca–N intermediates requires carefully tuning the reaction environment—specifically by replacing THF with dimethoxyethane (DME), which dramatically reduces solvent degradation. A custom flow-cell reactor with high–surface-area Ni foam electrodes further enhances nitrogen availability and improves long-term operation. Using in-situ Raman spectroscopy and XPS, we directly captured the formation and stabilization of calcium nitride, offering rare mechanistic visibility into a pathway that has long been difficult to probe. These insights illuminate how solvent coordination, electrode chemistry, and interfacial mass transfer govern both intermediate stability and ammonia productivity. The result is a system that sets new benchmarks for ambient ammonia electrosynthesis—achieving 34.35% Faradaic efficiency, sustaining ~20% efficiency over 56 hours, and reaching ammonia partial current densities up to 219 mA cm⁻². This work not only advances calcium-mediated nitrogen fixation but also provides a foundational mechanistic framework to guide the design of next-generation electrochemical ammonia technologies. Congratulations to Ishita Goyal, Ph.D. (lead author) and co-authors Hasiya Najmin Isa, Vamsi Vikram Gande, and Dr. Rohit Chauhan for driving this groundbreaking work forward. Your contributions are helping shape the future of sustainable ammonia production. #Electrochemistry #NitrogenFixation #AmmoniaSynthesis #ElectrochemicalAmmonia #SustainableChemistry

🔬⚡️ Electrochemistry in Synthesis: Pioneering Sustainable Innovation Electrochemistry can revolutionize chemical synthesis across industries by offering precise control, green chemistry solutions, and access to novel compounds. Here's why it matters: 1.    Selective Synthesis: With precise control over potentials and currents, electrochemistry allows for selective reactions that are often challenging with traditional methods. 2.    Green Chemistry: By using electricity as the primary reagent, electrochemical processes reduce reliance on hazardous chemicals, aligning with sustainability goals. 3.    Functional Group Tolerance: Electrochemical methods tolerate a wide range of functional groups, preserving sensitive parts of molecules in complex synthesis. 4.    Mild Reaction Conditions: Operating under mild temperatures and pressures, electrochemistry reduces energy consumption and improves safety. 5.    Access to Novel Compounds: It enables synthesis of compounds difficult to obtain via traditional means, driving innovation in pharmaceuticals, materials science, and more. However, scaling up electrochemical processes presents unique challenges: ·      Electrode Design: Ensuring efficient mass transfer and electrode stability at larger scales. ·      Process Optimization: Adapting conditions for consistent performance across batch sizes. ·      Economic Viability: Balancing initial setup costs with long-term benefits of efficiency and sustainability. As we explore these frontiers, electrochemistry emerges not just as a tool for synthesis, but as a cornerstone of sustainable and innovative chemical manufacturing. Let's continue pushing boundaries for a cleaner, more efficient future. #Electrochemistry #GreenChemistry #ChemicalSynthesis #Sustainability

Lithium extraction from seawater not only holds the key to satisfying the escalating global demand for lithium due to its vast reserves but also challenges us with its technical complexities. In recent research by Liu C. et al, electrochemical intercalation has emerged as a cutting-edge method to tackle these challenges, particularly with the pulsed electrochemical techniques that enhance the selectivity of lithium over sodium, a common and problematic impurity. The ocean contains lithium at a dilute concentration of appx 0.180 parts per million (ppm), overshadowed by sodium's overwhelming presence at about 10,800 ppm. This stark contrast poses a significant hurdle in selectively mining lithium without capturing excessive sodium. The innovative approach developed in recent studies involves pulsed-rest & pulse-rest-reverse pulse-rest electrochemical methods, utilizing TiO2-coated FePO4 electrodes to dramatically enhance lithium selectivity. These methods effectively reduce the overpotential required for lithium intercalation into FePO4, a critical factor for improving the economic feasibility of the extraction process. The pulsed electrochemical techniques operate on the principle of intermittently applying current, which allows for periods of rest. During these rest periods, the system rebalances, which helps in managing the intercalation of lithium ions more selectively than sodium ions. The unique aspect of the method is its ability to maintain the crystal structure stability of the electrode material throughout the extraction process, thus prolonging its operational life and efficiency. The electrodes used are particularly designed with a TiO2 coating to improve interface contact with seawater, thereby enhancing the electrochemical interaction necessary for selective lithium recovery. Initial tests demonstrated a promising Li to Na recovery ratio of 1:1, a significant achievement given the natural abundance ratios in seawater. Moreover, this method has been tested over multiple cycles, showing a consistent ability to recover lithium effectively with minimal degradation in performance. The challenge remains in scaling this technology. The process's energy efficiency, the durability of the electrodes under continuous operation, and the potential environmental impacts of large-scale seawater processing need thorough assessment. However, the groundwork laid by these innovative electrochemical techniques provides a hopeful outlook for the future of lithium extraction from seawater. #lithiumionbatteries #electricvehicles #batteries Reference: Liu, C., Li, Y., Lin, D., Hsu, P.C., Liu, B., Yan, G., Wu, T., Cui, Y. and Chu, S., 2020. Lithium extraction from seawater through pulsed electrochemical intercalation. Joule, 4(7), pp.1459-1469.

Excited to share that our latest work has just been published in Nano Letters 🎉. This is also my first work at Stanford. In this study, we show that you can use epitaxial electrodeposition in aqueous electrolytes to grow highly oriented Fe on Cu substrates and actively control the in-plane variants by choosing different Cu crystal facets (Cu(111), Cu(100), Cu(110)). This crystallographic control leads to: • Much denser and smoother Fe deposits • Suppressed dendritic growth and reduced HER • Significantly higher Coulombic efficiency and longer cycle life for Fe metal anodes in water-based systems Although the work is framed around water-based Fe metal anodes for large-scale energy storage, the concept is more general: it shows how low-temperature, solution-based epitaxial electrodeposition can be used as a tool to engineer metal films with controlled texture and orientation. This has interesting implications not only for batteries, safe power supply for data center, but also for advanced semiconductor manufacturing, where electroplating is central to metal interconnects, TSVs, and high-aspect-ratio gap fill. Being able to “grow” more ordered, orientation-controlled metal films electrochemically could open new paths for performance and reliability in those processes as well. Grateful to work with an incredible team on this project: Ching-Tai (Vincent) Fu, Guangxia Feng, Yuqi Li , Junyan Li, Gangbin Yan, my Ph. D. advisor Prof. Po-Chun Hsu, Prof. Steven Chu, and and mostly grateful for my Postdoc advisor Prof. Yi Cui. For those interested, the article is available here (free e-print link, limited uses): https://lnkd.in/gc727nwT

Proud to announce another publication from our ongoing collaboration with Pfizer Process Chemistry (US) in the field of electroorganic synthesis. In this project the electrochemical synthesis of a key thiol intermediate in the preparation of axitinib has been achieved using a modified spinning cylinder electrode reactor adapted for “quasi-divided” cell operation. This concept enables the target cathodic reduction to occur without the need for sacrificial electrodes or divided cells equipped with ion exchange membranes (https://shorturl.at/BCGUX). This work is a continuation of our ongoing efforts to develop scalable reactor technology for electroorganic synthesis based on the spinning electrode concept. This technology permits scaling electrochemical transformations from the milligram scale to kilogram quantities without the need for re‑optimization of reaction conditions. The reactor can operate both in batch and continuous mode, can process slurries and handle gas evolution. Check out the original publication here: https://lnkd.in/dX_gS-8n. Great collaboration with Eric Hansen, Caleb Kong, Joseph Imbrogno, Jenson Verghese, Steven Guinness, Chase Salazar and Jean-Nicolas (Nick) Desrosiers at Pfizer. The reactor has been developed by Bhanwar Malviya and David Cantillo at Karl-Franzens-Universität Graz and Research Center Pharmaceutical Engineering GmbH. #electrochemistry #continuousmanufacturing #activepharmaceuticalingredients #greenchemistry