Advanced Electroanalysis for Electrosynthesis.

Electrosynthesis is a popular, environmentally friendly substitute for conventional organic methods. It involves using charge transfer to stimulate chemical reactions through the application of a potential or current between two electrodes. In addition to electrode materials and the type of reactor employed, the strategies for controlling potential and current have an impact on the yields, product distribution, and reaction mechanism. In this Review, recent advances related to electroanalysis applied in electrosynthesis were discussed. The first part of this study acts as a guide that emphasizes the foundations of electrosynthesis. These essentials include instrumentation, electrode selection, cell design, and electrosynthesis methodologies. Then, advances in electroanalytical techniques applied in organic, enzymatic, and microbial electrosynthesis are illustrated with specific cases studied in recent literature. To conclude, a discussion of future possibilities that intend to advance the academic and industrial areas is presented.

Scanning Electrochemical Microscopy Reveals That Model Silicon Anodes Demonstrate Global Solid Electrolyte Interphase Passivation Degradation during Calendar Aging.

Silicon is a promising next-generation anode to increase energy density over commercial graphite anodes, but calendar life remains problematic. In this work, scanning electrochemical microscopy was used to track the site-specific reactivity of a silicon thin film surface over time to determine if undesirable Faradaic reactions were occurring at the formed solid electrolyte interphase (SEI) during calendar aging in four case scenarios: formation between 1.5 V and 100 mV with subsequent rest starting at (1) 1.5 V and (2) 100 mV and formation between 0.75 V and 100 mV with subsequent rest starting at (3) 0.75 V and (4) 100 mV. In all cases, the electrical passivation of silicon decreased with increasing time and potential relative to Li/Li+ over a 3 day period. Along with the decrease in passivation, the homogeneity of passivation over a 500 µm2 area decreased with time. Despite some local "hot spots" of reactivity, the areal uniformity of passivation suggests global SEI failure (e.g., SEI dissolution) rather than localized (e.g., cracking) failure. The silicon delithiated to 1.5 V vs Li/Li+ was less passivated than the lithiated silicon (at the beginning of rest, the forward rate constants, kf, for ferrocene redox were 7.19 × 10-5 and 3.17 × 10-7 m/s, respectively) and was also found to be more reactive than the pristine silicon surface (kf of 5 × 10-5 m/s). This reactivity was likely the result of SEI oxidation. When the cell was only delithiated up to 0.75 V versus Li/Li+, the surface was still passivating (kf of 6.11 × 10-6 m/s), but still less so than the lithiated surface (kf of 3.03 × 10-9 m/s). This indicates that the potential of the anode should be kept at or below ∼0.75 V vs Li/Li+ to prevent decreasing SEI passivation. This information will help with tuning the voltage windows for prelithiation in Si half cells and the operating voltage of Si full cells to optimize calendar life. The results provided should encourage the research community to investigate chemical, rather than mechanical, modes of failure during calendar aging and to stop using the typical convention of 1.5 V as a cutoff potential for cycling Si in half cells.

Extracellular Poly(hydroxybutyrate) Bioplastic Production Using Surface Display Techniques.

Poly(hydroxybutyrate) is a biocompatible, biodegradable polyester synthesized naturally in a variety of microbial species. A greener alternative to petroleum-based plastics and sought after for biomedical applications, poly(hydroxybutyrate) has failed to break through as a leading material in the plastic industry due to its high cost of production. Specifically, the extraction of this material from within bacterial cells requires lysis of cells, which takes time, uses harsh chemicals, and starts the process again with growing new living cells. Recently, surface display of enzymes on bacterial membranes has become an emerging technique for extracellular biocatalysis. In this work, a fusion protein lpp-ompA-phaC was expressed in Escherichia coli to display the enzyme poly(hydroxyalkanoate) synthase on the cell surface. The resulting poly(hydroxybutyrate) product was chemically characterized by nuclear magnetic resonance and infrared spectroscopy. Finally, the extracellular synthesis of the bioplastic granules was demonstrated qualitatively via microscopy and quantitatively by flow cytometry. The results of this work are the first demonstration of extracellular synthesis of poly(hydroxybutyrate), showing promise for continuous and scalable synthesis of materials using surface display.

Electrocatalytic Asymmetric Nozaki-Hiyama-Kishi Decarboxylative Coupling: Scope, Applications, and Mechanism.

The first general enantioselective alkyl-Nozaki-Hiyama-Kishi (NHK) coupling reactions are disclosed herein by employing a Cr-electrocatalytic decarboxylative approach. Using easily accessible aliphatic carboxylic acids (via redox-active esters) as alkyl nucleophile synthons, in combination with aldehydes and enabling additives, chiral secondary alcohols are produced in a good yield with high enantioselectivity under mild reductive electrolysis. This reaction, which cannot be mimicked using stoichiometric metal or organic reductants, tolerates a broad range of functional groups and is successfully applied to dramatically simplify the synthesis of multiple medicinally relevant structures and natural products. Mechanistic studies revealed that this asymmetric alkyl e-NHK reaction was enabled by using catalytic tetrakis(dimethylamino)ethylene, which acts as a key reductive mediator to mediate the electroreduction of the CrIII/chiral ligand complex.

Phenyl Acrylate-Based Cross-Linked Anion Exchange Membranes for Non-aqueous Redox Flow Batteries.

Redox flow batteries (RFBs) are of recent interest to store harvested renewable energy for improving grid reliability and utilization. In this study, we synthesized and characterized a series of phenyl acrylate-based UV-cross-linked anion exchange membranes (AEMs) and explored the performance of these AEMs in a model non-aqueous RFB under model conditions. Infrared spectroscopy was utilized to confirm the incorporation of ion carriers in the phenyl acrylate backbone. The electrochemical performance was compared with the commercial Fumasep membrane Fuma-375 based on high stability in non-aqueous solvents, high permeability to the charge-carrying ion, low resistance, low crossover of the redox-active molecules, and low cost. Our results show 55% total capacity retention through 1000 charge/discharge cycles because of low crossover as compared to the Fumasep commercial membrane which retained only 28% capacity. This result is promising in understanding and developing next-generation AEMs for non-aqueous RFBs and other electrochemical systems utilizing organic solvents.

Advances in Bioelectrode Design for Developing Electrochemical Biosensors.

The critical performance factors such as selectivity, sensitivity, operational and storage stability, and response time of electrochemical biosensors are governed mainly by the function of their key component, the bioelectrode. Suitable design and fabrication strategies of the bioelectrode interface are essential for realizing the requisite performance of the biosensors for their practical utility. A multifaceted attempt to achieve this goal is visible from the vast literature exploring effective strategies for preparing, immobilizing, and stabilizing biorecognition elements on the electrode surface and efficient transduction of biochemical signals into electrical ones (i.e., current, voltage, and impedance) through the bioelectrode interface with the aid of advanced materials and techniques. The commercial success of biosensors in modern society is also increasingly influenced by their size (and hence portability), multiplexing capability, and coupling in the interface of the wireless communication technology, which facilitates quick data transfer and linked decision-making processes in real-time in different areas such as healthcare, agriculture, food, and environmental applications. Therefore, fabrication of the bioelectrode involves careful selection and control of several parameters, including biorecognition elements, electrode materials, shape and size of the electrode, detection principles, and various fabrication strategies, including microscale and printing technologies. This review discusses recent trends in bioelectrode designs and fabrications for developing electrochemical biosensors. The discussions have been delineated into the types of biorecognition elements and their immobilization strategies, signal transduction approaches, commonly used advanced materials for electrode fabrication and techniques for fabricating the bioelectrodes, and device integration with modern electronic communication technology for developing electrochemical biosensors of commercial interest.

Unraveling Hydrogen Atom Transfer Mechanisms with Voltammetry: Oxidative Formation and Reactivity of Cobalt Hydride.

The utility of transition metal hydride catalyzed hydrogen atom transfer (MHAT) has been widely demonstrated in organic transformations such as alkene isomerization and hydrofunctionalization reactions. However, the highly reactive nature of the hydride and radical intermediates has hindered mechanistic insight into this pivotal reaction. Recent advances in electrochemical MHAT have opened up the possibility for new analytical approaches for mechanistic diagnosis. Here, we report a voltammetric interrogation of Co-based MHAT reactivity, describing in detail the oxidative formation and reactivity of the key Co-H intermediate and its reaction with aryl alkenes. Insights from cyclic voltammetry and finite element simulations help elucidate the rate-limiting step as metal hydride formation, which we show to be widely tunable based on ligand design. Voltammetry is also suggestive of the formation of Co-alkyl intermediates and a dynamic equilibrium with the reactive neutral radical. These mechanistic studies provide information for the design of future hydrofunctionalization reactions, such as catalyst and silane choice, the relative stability of metal-alkyl species, and how hydrofunctionalization reactions utilize Co-alkyl intermediates. In summary, these studies establish an important template for studying MHAT reactions from the perspective of electrochemical kinetic frameworks.

Resonance Raman spectra and excited state properties of methyl viologen and its radical cation from time-dependent density functional theory.

Time-dependent density functional theory (TDDFT) was applied to gain insights into the electronic and vibrational spectroscopic properties of an important electron transport mediator, methyl viologen (MV2+ ). An organic dication, MV2+ has numerous applications in electrochemistry that include energy conversion and storage, environmental remediation, and chemical sensing and electrosynthesis. MV2+ is easily reduced by a single electron transfer to form a radical cation species (MV•+ ), which has an intense UV-visible absorption near 600 nm. The redox properties of the MV2+ /MV•+ couple and light-sensitivity of MV•+ have made the system appealing for photo-electrochemical energy conversion (e.g., solar hydrogen generation from water) and the study of photo-induced charge transfer processes through electronic absorption and resonance Raman spectroscopic measurements. The reported work applies leading TDDFT approaches to investigate the electronic and vibrational spectroscopic properties of MV2+ and MV•+ . Using a conventional hybrid exchange functional (B3-LYP) and a long-range corrected hybrid exchange functional (ωB97X-D3), including with a conductor-like polarizable continuum model to account for solvation, the electronic absorption and resonance Raman spectra predicted are in good agreement with experiment. Also analyzed are the charge transfer character and natural transition orbitals derived from the TDDFT vertical excitations calculated. The findings and models developed further the understanding of the electronic properties of viologens and related organic redox mediators important in renewable energy applications and serve as a reference for guiding the interpretation of electronic absorption and Raman spectra of the ions.

Understanding Formation and Roles of NiII Aryl Amido and NiIII Aryl Amido Intermediates in Ni-Catalyzed Electrochemical Aryl Amination Reactions.

Ni-catalyzed electrochemical aryl amination (e-amination) is an attractive, emerging approach to building C-N bonds. Here, we report in-depth experimental and computational studies that examined the mechanism of Ni-catalyzed e-amination reactions. Key NiII-amine dibromide and NiII aryl amido intermediates were chemically synthesized and characterized. The combination of experiments and DFT calculations suggest (1) there is coordination of an amine to the NiII catalyst before the cathodic reduction and oxidative addition steps, (2) a stable NiII aryl amido intermediate is produced from the cathodic half-reaction, a critical step in controlling the selectivity between cross-coupling and undesired homo-coupling reaction pathways, (3) the diazabicycloundecene additive shifts the aryl halide oxidative addition mechanism from a NiI-based pathway to a Ni0-based pathway, and (4) redox-active bromide in the supporting electrolyte functions as a redox mediator to promote the oxidation of the stable NiII aryl amido intermediate to a NiIII aryl amido intermediate. Subsequently, the NiIII aryl amido intermediate undergoes facile reductive elimination to provide a C-N cross-coupling product at room temperature. Overall, our results provide new fundamental understandings about this e-amination reaction and guidance for further development of other Ni-catalyzed electrosynthetic reactions such as C-C and C-O cross-couplings.

Detection of Acetaminophen in Groundwater by Laccase-Based Amperometric Biosensors Using MoS2 Modified Carbon Paper Electrodes.

The use of enzyme-based biosensors for the detection and quantification of analytes of interest such as contaminants of emerging concern, including over-the-counter medication, provides an attractive alternative compared to more established techniques. However, their direct application to real environmental matrices is still under investigation due to the various drawbacks in their implementation. Here, we report the development of bioelectrodes using laccase enzymes immobilized onto carbon paper electrodes modified with nanostructured molybdenum disulfide (MoS2). The laccase enzymes were two isoforms (LacI and LacII) produced and purified from the fungus Pycnoporus sanguineus CS43 that is native to Mexico. A commercial purified enzyme from the fungus Trametes versicolor (TvL) was also evaluated to compare their performance. The developed bioelectrodes were used in the biosensing of acetaminophen, a drug widely used to relieve fever and pain, and of which there is recent concern about its effect on the environment after its final disposal. The use of MoS2 as a transducer modifier was evaluated, and it was found that the best detection was achieved using a concentration of 1 mg/mL. Moreover, it was found that the laccase with the best biosensing efficiency was LacII, which achieved an LOD of 0.2 µM and a sensitivity of 0.108 µA/µM cm2 in the buffer matrix. Moreover, the performance of the bioelectrodes in a composite groundwater sample from Northeast Mexico was analyzed, achieving an LOD of 0.5 µM and a sensitivity of 0.015 µA/µM cm2. The LOD values found are among the lowest reported for biosensors based on the use of oxidoreductase enzymes, while the sensitivity is the highest currently reported.

Bioelectrocatalytic Synthesis: Concepts and Applications.

Bioelectrocatalytic synthesis is the conversion of electrical energy into value-added products using biocatalysts. These methods merge the specificity and selectivity of biocatalysis and energy-related electrocatalysis to address challenges in the sustainable synthesis of pharmaceuticals, commodity chemicals, fuels, feedstocks and fertilizers. However, the specialized experimental setups and domain knowledge for bioelectrocatalysis pose a significant barrier to adoption. This review introduces key concepts of bioelectrosynthetic systems. We provide a tutorial on the methods of biocatalyst utilization, the setup of bioelectrosynthetic cells, and the analytical methods for assessing bioelectrocatalysts. Key applications of bioelectrosynthesis in ammonia production and small-molecule synthesis are outlined for both enzymatic and microbial systems. This review serves as a necessary introduction and resource for the non-specialist interested in bioelectrosynthetic research.

Exploring electrolyte effects on metal-alkyl bond stability: impact and implications for electrosynthesis.

Transition metal catalysis hinges on the formation of metal-carbon bonds during catalytic cycles. The stability and reactivity of these bonds are what determine product chemo-, regio-, and enantioselectivity. The advent of electrosynthetic methodologies has placed the current understanding of these metal-alkyl bonds into a new environment of charged species and electrochemically induced reactivity. In this paper, we explore the often neglected impact of supporting electrolyte on homogeneous electrocatalytic mechanisms using the catalytic reduction of benzyl chlorides via Co and Fe tetraphenylporphyrins as a model reaction. The mechanism of this reaction is confirmed to proceed through the formation of the metal-alkyl intermediates. Critically, the stability of these intermediates, in both the Co and Fe systems, is found to be affected by the hydrodynamic radius of the supporting electrolyte, leading to differences in electrolyte-solvent shell. These studies provide important information for the design of electrosynthetic reactions, and provide a starting point for the rational design of functional supporting electrolytes.

In Situ Confocal Raman Microscopy of Redox Polymer Films on Bulk Electrode Supports.

A spectroelectrochemical cell is described that enables confocal Raman microscopy studies of electrode-supported films. The confocal probe volume (∼1 µm3) was treated as a fixed-volume reservoir for the observation of potential-induced changes in chemical composition at microscopic locations within an ∼20 µm thickness layer of a redox polymer cast onto a 3 mm diameter carbon disk electrode. Using a Raman system with high collection efficiency and wavelength reproducibility, spectral subtraction achieved excellent rejection of background interferences, opening opportunities for measuring within micrometer-scale thickness redox films on widely available, low-cost, and conventional carbon disk electrodes. The cell performance and spectral difference technique are demonstrated in experiments that detect transformations of redox-active molecules exchanged into electrode-supported ionomer membranes. The in situ measurements were sensitive to changes in the film oxidation state and swelling/deswelling of the polymer framework in response to the uptake and discharge of charge-compensating electrolyte ions. The studies lay a foundation for confocal Raman microscopy as a quantitative in situ probe of processes within electrode-immobilized redox polymers under development for a range of applications, including electrosynthesis, energy conversion, and chemical sensing.

Biological anolyte regeneration system for redox flow batteries.

Redox flow battery (RFB) electrolyte degradation is a common failure mechanism in RFBs. We report an RFB using genetically engineered, phenazine-producing Escherichia coli to serve as an anolyte regeneration system capable of repairing the degraded/decomposed redox-active phenazines. This work represents a new strategy for improving the stability of RFB systems because, under the influence of genetically engineered microbes, the anolyte species does not display degradation after battery cycling.