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Herein, we describe an innovative approach to the asymmetric electrochemical α‐alkylation of aldehydes facilitated by a newly designed bifunctional chiral electrocatalyst. The highly efficient bifunctional chiral electrocatalyst combines a chiral aminocatalyst with a redox mediator. It plays a dual role as a redox mediator for electrooxidation, while simultaneously providing remarkable asymmetric induction for the stereoselective α‐alkylation of aldehydes. Additionally, this novel catalyst exhibits enhanced catalytic activity and excellent stereoselective control comparable to conventional catalytic systems. As a result, this strategy provides a new avenue for versatile asymmetric electrochemistry. The electrooxidation of diverse phenols enables the C−H/C−H oxidative α‐alkylation of aldehydes in a highly chemo‐ and stereoselective fashion. Detailed mechanistic studies by control experiments and cyclic voltammetry analysis demonstrate possible reaction pathways and the origin of enantio‐induction. [ABSTRACT FROM AUTHOR]

Carbon‐based materials have been utilized as effective catalysts for hydrogen peroxide electrosynthesis via two‐electron oxygen reduction reaction (2e ORR), however the insufficient selectivity and productivity still hindered the further industrial applications. In this work, we report the Fe−O4 motif activated graphitic carbon material which enabled highly selective H2O2 electrosynthesis operating at high current density with excellent anti‐poisoning property. In the bulk production test, the concentration of H2O2 cumulated to 8.6 % in 24 h and the corresponding production rate of 33.5 mol gcat−1 h−1 outperformed all previously reported materials. Theoretical model backed by in situ characterization verified α‐C surrounding the Fe−O4 motif as the actual reaction site in terms of thermodynamics and kinetics aspects. The strategy of activating carbon reaction site by metal center via oxo‐bridge provides inspiring insights for the rational design of carbon materials for heterogeneous catalysis. [ABSTRACT FROM AUTHOR]

Electrocatalytic nitrate reduction reaction (NO3RR) coupled with organic compounds to synthesize oximes for value-added conversion of waste pollutants has very promising prospects. However, due to the susceptibility of the feedstock to hydrogenation, the relatively low reaction efficiency, and the poor stability of oximes, the reaction in acidic electrolytes remains a formidable challenge. Herein, we report a novel strategy for the one-step synthesis of oximes from nitrite and aldehydes/ketones in acidic electrolytes using a Zn-based catalyst (multilayered Zn nanosheet catalyst, M-ZnNSs). 99% yield and 99% selectivity of phenylacetaldehyde oxime were achieved at a constant current of -12 mA cm-2. Moreover, various aldehydes/ketones were efficiently converted to oximes with yield and selectivity up to >90%, demonstrating the high versatility of this method. Furthermore, the catalyst exhibited remarkable long-term stability (>100 h). This work proposes a green strategy to promote the recycling of nitrogen resources, enhance the value of NO3- conversion products, and develop new ideas for electrochemical C-N coupling. [ABSTRACT FROM AUTHOR]

Electrochemical CO2 reduction (ECR) holds great potential to alleviate the greenhouse effect and our dependence on fossil fuels by integrating renewable energy for the electrosynthesis of high-value fuels from CO2. However, the high thermodynamic energy barrier, sluggish reaction kinetics, inadequate CO2 conversion rate, poor selectivity for the target product, and rapid electrocatalyst degradation severely limit its further industrial-scale application. Although numerous strategies have been proposed to enhance ECR performances from various perspectives, scattered studies fail to comprehensively elucidate the underlying effect-performance relationships toward ECR. Thus, this review presents a comparative summary and a deep discussion with respect to the effects strongly-correlated with ECR, including intrinsic effects of materials caused by various sizes, shapes, compositions, defects, interfaces, and ligands; structure-induced effects derived from diverse confinements, strains, and fields; electrolyte effects introduced by different solutes, solvents, cations, and anions; and environment effects induced by distinct ionomers, pressures, temperatures, gas impurities, and flow rates, with an emphasis on elaborating how these effects shape ECR electrocatalytic activities and selectivity and the underlying mechanisms. In addition, the challenges and prospects behind different effects resulting from various factors are suggested to inspire more attention towards high-throughput theoretical calculations and in situ/operando techniques to unlock the essence of enhanced ECR performance and realize its ultimate application. [ABSTRACT FROM AUTHOR]

This study reports ambient electrosynthesis of dimethyl carbonate with a palladium–gold catalyst. Material screening identifies a region of intermediate‐catalyst binding energy that facilitates interfacial electron and proton transfers for selective carbonylation, achieving a distinct maximum of 92% faradaic efficiency to dimethyl carbonate. Structural and electrochemical analyses suggest that the alloying of palladium and gold effectively modulates the CO* binding energy to the catalytic surface, in accord with subsequent computational studies. With an extended heterogeneous–homogeneous catalytic environment with a halide redox mediator, a remarkable partial current density of 52 mA cm−2 is observed for dimethyl carbonate for 100 h of continuous operation. [ABSTRACT FROM AUTHOR]

Enantioselective transformation of ubiquitous C(sp3)−H bonds into three‐dimensional chiral scaffolds is of longstanding interest to synthetic chemists. Herein, an asymmetric paired electrolysis enables a highly efficient and sustainable approach to the enantioselective alkylation of sulfonylimines via C(sp3)−H functionalization. In this protocol, anodic oxidation for benzylic radical formation and Lewis acid‐catalyzed sulfonylimine reduction on the cathode were seamlessly cross‐coupled (up to 88 % yield). Enantioenriched chiral amines containing a tetrasubstituted carbon stereocenter are accessed with high enantioselectivity (up to 96 % ee). Mechanistic studies suggest that the amine generated in situ could serve as a base to deprotonate phenols and decrease the oxidation potential of the reaction, allowing phenols with lower potentials to be preferentially oxidized. [ABSTRACT FROM AUTHOR]

Phosphorene and fullerene are representative two‐dimensional (2D) and zero‐dimensional (0D) nanomaterials respectively, constructing their heterodimensional hybrid not only complements their physiochemical properties but also extends their applications via synergistic interactions. This is however challenging because of their diversities in dimension and chemical reactivity, and theoretical studies predicted that it is improbable to directly bond C60 onto the surface of phosphorene due to their strong repulsion. Here, we develop a facile electrosynthesis method to synthesize the first phosphorene‐fullerene hybrid featuring fullerene surface bonding via P−C bonds. Few‐layer black phosphorus nanosheets (BPNSs) obtained from electrochemical exfoliation react with C602− dianion prepared by electroreduction of C60, fulfilling formation of the "improbable" phosphorene‐fullerene hybrid (BPNS‐s‐C60). Theoretical results reveal that the energy barrier for formation of [BPNS‐s‐C60]2− intermediate is significantly decreased by 1.88 eV, followed by an oxidization reaction to generate neutral BPNS‐s‐C60 hybrid. Surface bonding of C60 molecules not only improves significantly the ambient stability of BPNSs, but also boosts dramatically the visible light and near‐infrared (NIR) photocatalytic hydrogen evolution rates, reaching 1466 and 1039 μmol h−1 g−1 respectively, which are both the highest values among all reported BP‐based metal‐free photocatalysts. [ABSTRACT FROM AUTHOR]

Cross‐electrophile coupling (XEC) between aryl halides and alkyl halides is a streamlined approach for C(sp2)−C(sp3) bond construction, which is highly valuable in medicinal chemistry. Based on a key NiII aryl amido intermediate, we developed a highly selective and scalable Ni‐catalyzed electrochemical XEC reaction between (hetero)aryl halides and primary and secondary alkyl halides. Experimental and computational mechanistic studies indicate that an amine secondary ligand slows down the oxidative addition process of the Ni‐polypyridine catalyst to the aryl bromide and a NiII aryl amido intermediate is formed in situ during the reaction process. The relatively slow oxidative addition is beneficial for enhancing the selectivity of the XEC reaction. The NiII aryl amido intermediate stabilizes the NiII–aryl species to prevent the aryl–aryl homo‐coupling side reactions and acts as a catalyst to activate the alkyl bromide substrates. This electrosynthesis system provides a facile, practical, and scalable platform for the formation of (hetero)aryl–alkyl bonds using standard Ni catalysts under mild conditions. The mechanistic insights from this work could serve as a great foundation for future studies on Ni‐catalyzed cross‐couplings. [ABSTRACT FROM AUTHOR]

The electrocatalytic nitrate reduction reaction (NO3−RR) presents a promising pathway for achieving both ammonia (NH3) electrosynthesis and water pollutant removal simultaneously. Among various electrocatalysts explored, 2D materials have emerged as promising candidates due to their ability to regulate electronic states and active sites through doping. However, the impact of doping effects in 2D materials on the mechanism of NO3−RR remains relatively unexplored. Here, Ni‐doped MoS2 (Ni‐MoS2) nanosheets are investigated as a model system, demonstrating enhanced NO3−RR performance compared to undoped counterparts. By controlling the doping concentration, the Ni‐MoS2 nanosheets achieve a remarkable faradic efficiency (FE) of 92.3% for NH3 at −0.3 VRHE with excellent stability. The mechanistic studies reveal that the elevation of the NO3−RR performances originates from the generation of more active hydrogen and the acceleration of the reaction from nitrite (NO2−) to NH3 facilitated by Ni doping. Combining the experimental observations and theoretical calculations it is revealed that the appropriate Ni doping level in MoS2 can enhance *NO3 adsorption strength, thereby facilitating subsequent electrocatalytic steps. Together with the demonstration of Zn−NO3− and Zn−NO2− battery devices, the work provides new insights into the design and regulation of the active sites in 2D material catalysts for efficient NO3−RR. [ABSTRACT FROM AUTHOR]

• A novel side-aerated reactor for in-situ H 2 O 2 electrosynthesis was designed. • Side-aerated reactor coupled with a composite cathode greatly improved H 2 O 2 production. • Different aeration system and cathodes were evaluated for comparison. • Key factors for in-situ H 2 O 2 electrosynthesis were determined. The active graphite felt (GF) catalytic layer was effectively synthesized through a wet ultrasonic impregnation-calcination method, modified with CB and PTFE, and implemented in a pioneering side-aeration electrochemical in-situ H 2 O 2 reactor. The optimal mass ratio (CB: PTFE 1:4) for the modified cathode catalytic layer was determined using a single-factor method. Operating under optimum conditions of initial pH 5, 0.5 L/min air flow, and a current density of 9 mA/cm2, the system achieved a remarkable maximum H 2 O 2 accumulation of 560 mg/L, with the H 2 O 2 production capacity consistently exceeding 95 % over 6 usage cycles. The refined mesoporous structure and improved three-phase interface notably amplified oxygen transfer, utilization, and H 2 O 2 yield. Side aeration led to an oxygen concentration near the cathode reaching 20 mg/L, representing a five-fold increase compared to the 3.95 mg/L achieved with conventional bottom aeration. In the final application, the reaction system exhibited efficacy in the degradation of landfill leachate concentrate. After a 60-minute reaction, complete removal of chroma was attained, and the TOC degradation rate surpassed 60 %, marking a sixfold improvement over the conventional system. These results underscore the substantial potential of the system in H 2 O 2 synthesis and environmental remediation. [ABSTRACT FROM AUTHOR]

Ni-doped CoTe nanorods have been prepared for 5-hydroxymethylfurfural oxidation reaction. The doping of Ni facilitates the oxidation of Co2+ to high-valent CoO 2 to achieve efficient electrosynthesis of the valuable 2,5-furandicarboxylic acid. [Display omitted] • A crude nanorod structure CoNiTe was prepared by two-step hydrothermal reactions for HMFOR. • Ni doping modulates the electronic structure of Co and improves the electrocatalytic performance of CoNiTe. • The generation of high-valent cobalt is the key for excellent HMFOR. Replacing the anodic oxygen evolution reaction (OER) in water splitting with 5-hydroxymethylfurfural oxidation reaction (HMFOR) can not only reduce the energy required for hydrogen production but also yield the valuable chemical 2,5-furandicarboxylic acid (FDCA). Co-based catalysts are known to be efficient for HMFOR, with high-valent Co being recognized as the main active component. However, efficiently promoting the oxidation of Co2+ to produce high-valent reactive species remains a challenge. In this study, Ni-doped CoTe (CoNiTe) nanorods were prepared as efficient catalysts for HMFOR, achieving a high HMFOR current density of 65.3 mA cm−2 at 1.50 V. Even after undergoing five successive electrolysis processes, the Faradaic efficiency (FE) remained at approximately 90.7 %, showing robust electrochemical durability. Mechanistic studies indicated that Ni doping changes the electronic configuration of Co, enhancing its charge transfer rate and facilitating the oxidation of Co2+ to high-valent CoO 2 species. This work reveals the effect of Ni doping on the reconfiguration of the active phase during HMFOR. [ABSTRACT FROM AUTHOR]

Electrochemical reduction of carbon dioxide to produce high-value ethylene is often limited by poor selectivity and yield of multi-carbon products. To address this, we propose a cyanamide-coordinated isolated copper framework with both metallic copper (Cu0) and charged copper (Cu1+) sites as an efficient electrocatalyst for the reduction of carbon dioxide to ethylene. Our operando electrochemical characterizations and theoretical calculations reveal that copper atoms in the Cuδ+NCN complex enhance carbon dioxide activation by improving surface carbon monoxide adsorption, while delocalized electrons around copper sites facilitate carbon-carbon coupling by reducing the Gibbs free energy for *CHC formation. This leads to high selectivity for ethylene production. The Cuδ+NCN catalyst achieves 77.7% selectivity for carbon dioxide to ethylene conversion at a partial current density of 400 milliamperes per square centimeter and demonstrates long-term stability over 80 hours in membrane electrode assembly-based electrolysers. This study provides a strategic approach for designing catalysts for the electrosynthesis of value-added chemicals from carbon dioxide. This study reports a cyanamide-framework stabilized multivalent copper catalyst for efficient electrochemical reduction of carbon dioxide to ethylene with 77.7% selectivity at 400 mA cm−2, offering a rational strategy for CO2 conversion. [ABSTRACT FROM AUTHOR]

Leveraging electrochemistry, a new synthesis of non‐natural derivatives of itaconic acid is proposed by utilizing carbon dioxide (CO2) as a valuable C1 synthon. An electrochemical cross‐electrophile coupling between allenoates and CO2 was targeted, allowing for the synthesis of both mono‐ and di‐carboxylation products in a catalyst‐ and additive‐free environment (yields up to 87 %, 30 examples). Elaboration of the model mono‐carboxylation product, and detailed cyclovoltammetric, as well as mechanistic analyses complete the present investigation. [ABSTRACT FROM AUTHOR]

We present the synthesis of a novel benzimidazolium-based surface active ionic liquid (SAIL), 3-dodecyl-1H-3λ-benzo[d]imidazole chloride, a SAIL with excellent surface activity and self-aggregation tendency whose aqueous micellar solutions offer exceptional solubilizing capacity and electrocatalytic performance for efficient electrocarboxylation of halocarbons. [ABSTRACT FROM AUTHOR]

A straightforward and efficient electrochemical method for the anodic oxidative selenenylation of 2-(2-arylallyl)phenols and a 2-(3-arylbut-3-en-1-yl)phenol with diselenides under ambient air conditions has been outlined. This method allows for the synthesis of selenyl-dihydrobenzofurans and a chromane featuring a sterically hindered tetrasubstituted carbon center, demonstrated through 25 examples with yields reaching up to 98%. Initial mechanistic investigations suggest the likely participation of pivotal seleniranium cation species in regulating the reactivity. [ABSTRACT FROM AUTHOR]

Leveraging electrochemistry, a new synthesis of non‐natural derivatives of itaconic acid is proposed by utilizing carbon dioxide (CO2) as a valuable C1 synthon. An electrochemical cross‐electrophile coupling between allenoates and CO2 was targeted, allowing for the synthesis of both mono‐ and di‐carboxylation products in a catalyst‐ and additive‐free environment (yields up to 87 %, 30 examples). Elaboration of the model mono‐carboxylation product, and detailed cyclovoltammetric, as well as mechanistic analyses complete the present investigation. [ABSTRACT FROM AUTHOR]

Hydrogen peroxide (H2O2) is a high-demand chemical, valued as a powerful and eco-friendly oxidant for various industrial applications. The traditional industrial method for producing H2O2, known as the anthraquinone process, is both costly and environmentally problematic. Electrochemical synthesis, which produces H2O2 using electricity, offers a sustainable alternative, particularly suited for small-scale, continuous on-site H2O2 generation due to the portability of electrocatalytic devices. For efficient H2O2 electrosynthesis, electrocatalysts must exhibit high selectivity, activity, and stability for the two-electron pathway-oxygen reduction reaction (2e− ORR). Transition-metal chalcogenide (TMC)-based materials have emerged as promising candidates for effective 2e− ORR due to their high activity in acidic environments and the abundance of their constituent elements. This review examines the potential of TMC-based catalysts in H2O2 electrosynthesis, categorizing them into noble-metal and non-noble-metal chalcogenides. It underscores the importance of achieving high selectivity, activity, and stability in 2e− ORR. By reviewing recent advancements and identifying key challenges, this review provides valuable insights into the development of TMC-based electrocatalysts for sustainable H2O2 production. [ABSTRACT FROM AUTHOR]

The article explores the electro-Fenton reaction as a sustainable method for removing persistent organic substances from wastewater. It discusses the species and reactions involved in the degradation process, emphasizing the fundamentals of electrochemistry, catalysis, and the reactivity of radicals. The article also presents simple experiments that can be used in the chemistry classroom to teach students about the electro-Fenton reaction. These experiments demonstrate the decomposition of organic dyes through electrolysis and confirm the formation of hydrogen peroxide and reactive radicals. The article discusses the potential applications of the electro-Fenton reaction in chemistry education and promotes sustainability. [Extracted from the article]

Ammonia (NH3) can be used as a fertilizer, a chemical or a new generation of fuel and has important agricultural and industrial value. Electrochemical NO3–-to-NH3 (NITRR) can realize the conversion of waste into treasure and waste resources, which is a promising method for ammonia synthesis. However, the process of NITRR is very complicated, resulting in product diversification and poor selectivity. In this work, an iron modified cerium oxide in rod form (Fe/CeO2-rod) catalysts was designed and used for the NITRR. The Fe/CeO2-rod catalyst showed excellent activity, and achieves high Faradaic efficiency (FE 95%) and NH3 yield rate (4.04 mg h–1 cm–2) in 0.1 M KOH electrolyte at – 0.52 V versus reversible hydrogen electrode. Furthermore, this catalyst exhibits a negligible activity decay during continuous electrolysis for 25 h. Further experiments provide the important role of Fe, which promote the formation of hydrogen radicals (H*). This study may provide new pathways to improve the activity of inexpensive catalysts for NITRR. [ABSTRACT FROM AUTHOR]

Electric discharge in deep-sea hydrothermal fields leads us to expect the existence of electroactive microbial ecosystems in the environments. Electrochemical properties such as electric field distribution on the seafloor and electrical conductivity of the rock can be useful indicators of searching electroactive microbial community in natural environments. We performed electric field measurements in deep-sea hydrothermal fields and collected rock samples by a remotely operative vehicle (ROV) operation. Several spots on the seafloor with strong electric fields were detected, which included both active hydrothermal vent areas and inactive sulfide deposits far from the vents. The electrical conductivity of the rock samples was correlated with the copper and iron sulfide content. Microbial community compositions of the rock samples were characterized by small subunit (SSU) rRNA gene amplicon sequencing analysis. The abundance of several microbial components, which are highly related to electroactive microorganisms such as Geobacteraceae and Thiomicrorhabdus, was affected by the electrical properties of rock samples. The results suggested that electrochemical properties on the seafloor would be related to the abundance of possible electroactive microbial populations, and that the electrochemical survey may be a powerful tool for exploring electroactive ecosystems. [ABSTRACT FROM AUTHOR]

We report an electrochemically promoted decarboxylation of readily available carboxylic acid and subsequent Mumm rearrangement to synthesize the corresponding imides. The reaction features external oxidant‐free, transition metal‐free mild conditions, and good functional group tolerance, affording various imides in moderate to good yields. Mechanistic studies reveal that the selective oxidation of aliphatic carboxylic acids appears to be the key step in this transformation. [ABSTRACT FROM AUTHOR]

The electrosynthesis of hydrogen peroxide (H2O2) via two‐electron oxygen reduction reaction (2e−‐ORR) enables high energy utilization and distributed H2O2 production. Rational catalyst design is essential for achieving efficient H2O2 production, in which fluorine‐modified carbon materials hold great potential. However, conventional methods can only induce limited loading of fluorine atoms in carbon‐based catalysts, leading to unsatisfying electrochemical performance. Herein, the design of fluorine‐containing active sites with high density and high 2e−‐ORR selectivity is achieved by loading fluorine‐containing chained polytetrafluoroethylene precursors onto conductive carbon substrates by plasma‐assisted ball milling technique. Consequently, the defect‐rich PTFE@CNTs show a high selectivity of over 95% and a high H2O2 yield of more than 35 mol g−1 h−1. Furthermore, the electrochemical production of H2O2 can be readily integrated with water purification units to decompose contaminants, showing over 80% degradation of multiple dyes within 1 h and over 95% removal ratio of antibiotics within 4 h. In addition, 100% sterilization of staphylococcus aureus is achieved by on‐site accumulating H2O2 in commercial saline for only 30 min. This defect engineering strategy through plasma ball milling provides a promising and universal avenue toward designing highly active and efficient electrocatalysts for 2e−‐ORR as well as other electrochemical processes. [ABSTRACT FROM AUTHOR]

Hydrogen peroxide (H2O2) is a highly desired chemical with a wide range of applications. Recent advancements in H2O2 synthesis center on the electrochemical reduction of oxygen, an environmentally friendly approach that facilitates on-site production. To successfully implement practical-scale, highly efficient electrosynthesis of H2O2, it is critical to meticulously explore both the design of catalytic materials and the engineering of other components of the electrochemical system, as they hold equal importance in this process. Development of promising electrocatalysts with outstanding selectivity and activity is a prerequisite for efficient H2O2 electrosynthesis, while well-configured electrolyzers determine the practical implementation of large-scale H2O2 production. In this review, we systematically summarize fundamental mechanisms and recent achievements in H2O2 electrosynthesis, including electrocatalyst design, electrode optimization, electrolyte engineering, reactor exploration, potential applications, and integrated systems, with an emphasis on active site identification and microenvironment regulation. This review also proposes new insights into the existing challenges and opportunities within this rapidly evolving field, together with perspectives on future development of H2O2 electrosynthesis and its industrial-scale applications. [ABSTRACT FROM AUTHOR]

Electrosynthesis of hydrogen peroxide (H2O2) based on proton exchange membrane (PEM) reactor represents a promising approach to industrial‐level H2O2 production, while it is hampered by the lack of high‐efficiency electrocatalysts in acidic medium. Herein, we present a strategy for the specific oxygen functional group (OFG) regulation to promote the H2O2 selectivity up to 92 % in acid on cobalt‐porphyrin molecular assembled with reduced graphene oxide. In situ X‐ray adsorption spectroscopy, in situ Raman spectroscopy and Kelvin probe force microscopy combined with theoretical calculation unravel that different OFGs exert distinctive regulation effects on the electronic structure of Co center through either remote (carboxyl and epoxy) or vicinal (hydroxyl) interaction manners, thus leading to the opposite influences on the promotion in 2e− ORR selectivity. As a consequence, the PEM electrolyzer integrated with the optimized catalyst can continuously and stably produce the high‐concentration of ca. 7 wt % pure H2O2 aqueous solution at 400 mA cm−2 over 200 h with a cell voltage as low as ca. 2.1 V, suggesting the application potential in industrial‐scale H2O2 electrosynthesis. [ABSTRACT FROM AUTHOR]

During the past decade, radical difluoromethylation has emerged as a powerful and versatile tool for the incorporation of difluoromethyl into various organic compounds. These reactions feature mild reaction conditions, very good functional group compatibilities, and quite broad substrate scopes, thus having drawn much attention and got rapid developments. A diverse range of difluoromethyl radical precursors have been developed for a series of radical difluoromethylation reactions. This review summarizes and discusses the advance in the radical difluoromethylation reactions, which are organized according to the protocols of generating difluoromethyl radical. [ABSTRACT FROM AUTHOR]

H2 produced via water electrolysis is a promising alternative to traditional energy, with electrodes playing a dominant role in the production process. To date, numerous studies have screened different types of biomass as precursors to synthesize electrocatalysts with practical functions, but the clear conclusions in this field are unfortunately absent. Therefore, herein, the recent advances in biomass-derived electrocatalysts for HER/OER processes are summarized, focusing on the design of carbonaceous structures from multiple components, the incorporation of supports with single or several metals and the available methods for their modification via defect engineering. Subsequently, the overall efficiency of electrochemical water splitting on a biomass-derived electrolyzer is discussed in depth together with the upgraded strategy for the so-called electrosynthesis of chemicals paired with H2 production. Finally, the technical bottlenecks that need to be properly resolved in the near future for the development of these electrocatalysts originating from biomass are presented. It can be expected that this review will not only contribute to the in-depth knowledge on the rational synthesis of biomass-derived materials as electrodes, but also present new opportunities for the valorization of biomass resources in electrochemical applications. [ABSTRACT FROM AUTHOR]

Urea electrosynthesis from co‐electrolysis of NO3− and CO2 (UENC) under ambient conditions is recognized as an appealing approach for effective and sustainable urea production, while it requires high‐efficiency UENC electrocatalysts to promote the C─N coupling and hydrogenation processes. Herein, single‐atom Cu anchored on MoS2 (Cu1‐MoS2) is explored as a highly active and selective UENC catalyst. Theoretical calculations and operando spectroscopic characterizations unveil the synergistic tandem catalysis of Cu1‐MoS2 for the UENC, where Cu single atoms trigger the early C─N coupling, while MoS2‐edges promote the key hydrogenation step of *CO2NH2 to *COOHNH2 for urea generation. Strikingly, Cu1‐MoS2 equipped in a flow cell achieves the excellent UENC performance with a maximum urea‐Faradaic efficiency of 57.02% at −0.6 V and the corresponding urea yield rate of 23.3 mmol h−1 g−1, surpassing nearly all previously reported UENC catalysts. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Organic fluorine compounds are ubiquitous and pivotally important organic molecules, yet their activation and transformation have long been a formidable challenge due to the high energy and low reactivity of C—F bonds. Organic electrosynthesis, an environmentally benign synthetic method in organic chemistry, enables a myriad of chemical transformations without the need for external redox reagents. In recent years, organic electrochemistry has emerged as a powerful tool for achieving the activation and transformation of C—F bonds in fluorine‐containing compounds. This review aims to succinctly recapitulate the latest advancements in the electrochemical defluorinative transformations of C—F bonds and to delve into the reaction design, mechanistic insights, and developmental prospects of these methods. Key Scientists: In 1959, Lund was the first to pioneer the electroreduction of CF3 to CH3 group. Electrochemistry has lately provided new opportunities for efficient conversion of organic fluorides. In 2020, Zhou and coworkers discovered the electrochemical defluorinative carboxylation of α‐CF3 alkenes. Lambert and colleagues reported electrophotocatalytic defluorinative amination of aryl fluorides. Electrochemical hydrodefluorination of trifluoromethylketones was developed by Lennox and coworkers in 2021. In the same year, Wang and Guo disclosed electrochemical radical defluorinative alkylation of α‐CF3 alkenes with Katritzky salts as the alkyl radical precursors. Subsequently, Wu and Liao described a transition‐metal‐free, site‐selective C—F arylation of polyfluoroarenes with (het)arenes using paired electrophotocatalysis. In 2023, numerous efforts were made to achieve electrochemical C—F bond activation. Xia and Guo developed an organoboron‐controlled method for the chemoselective electrochemical sequential (deutero)hydrodefluorination of trifluoroacetamides. [ABSTRACT FROM AUTHOR]

Integration of more thermodynamically favorable valorization of biomass (e.g., glycerol), compared to sluggish oxygen evolution, with H2 production is of great significance for energy‐saving electrosynthesis of value‐added chemicals. However, its widespread deployment has been challenged by costly electrocatalysts and large overpotential reaching an industrial‐relevant current density (≥400 mA cm−2). Herein, carbon shell‐encapsulated manganese‐doped cobalt nitride nanoarrays immobilizing on nickel foam, denoted Mn‐CoN@C/NF, are crafted via hydrothermal method and ammoniation. As a bifunctional electrocatalyst, the Mn‐CoN@C/NF manifests extraordinary activity for glycerol oxidation reaction (GOR) with an ultralow potential of 1.37 V (versus RHE) at 400 mA cm−2, in conjunction with H2 evolution reaction (HER) with a low overpotential of 31 mV at 10 mA cm−2. A record high Faradaic efficiency (97.7%) for formate production of GOR is delivered at 1.35 V (vs RHE). Impressively, a two‐electrode electrolyzer capitalizing on the Mn‐CoN@C/NF as catalysts reaches 800 mA cm−2 at 1.83 V, delivering an electricity‐saving efficiency of 15.0% compared to pure water splitting. DFT calculations substantiate that Mn species within Mn‐CoN not only optimize hydrogen adsorption kinetics for HER, but also elevate Co3+ active sites' density for GOR. This work offers an energy‐saving and efficient electrosynthesis avenue for coproduction of valuable chemicals. [ABSTRACT FROM AUTHOR]

Urea electrosynthesis from carbon dioxide (CO2) and nitrate (NO3−) is an alternative approach to traditional energy‐intensive urea synthesis technology. Herein, we report a CuAu single‐atom alloy (SAA) with electronic metal support interaction (EMSI), achieving a high urea yield rate of 813.6 μg h−1 mgcat−1 at −0.94 V versus reversible hydrogen electrode (vs. RHE) and a Faradaic efficiency (FE) of 45.2 % at −0.74 V vs. RHE. In situ experiments and theoretical calculations demonstrated that single‐atom Cu sites modulate the adsorption behavior of intermediate species. Bimetallic sites synergistically accelerate C−N bond formation through spontaneous coupling of *CO and *NO to form *ONCO as key intermediates. More importantly, electronic metal support interaction between CuAu SAA and CeO2 carrier further modulates electron structure and interfacial microenvironment, endowing electrocatalysts with superior activity and durability. This work constructs SAA electrocatalysts with EMSI effect to tailor C−N coupling at the atomic level, which can provide guidance for the development of C−N coupling systems. [ABSTRACT FROM AUTHOR]

N‐acyl iminophosphoranes have shown significant potentials in various areas. This paper presents two electrochemical strategies for the successful construction of a series of substituted N‐acyl iminophosphoranes using electrochemical activation of hydroxylamines or dioxazolones to generate unprotected amide radicals and radical anions. The simple undivided cell with inexpensive electrode setups (graphite felts, carbon rods, and copper sheets) provides excellent substrates tolerance under mild conditions. This simple electrochemical construction of N‐acyl iminophosphoranes also has good scalability, practicability and extensibility. Furthermore, synthetic transformations of the N‐acyl iminophosphorane products have demonstrated the application potentials of the P=N bond. [ABSTRACT FROM AUTHOR]

Hybrid materials with a rational organic-inorganic configuration can offer multifunctionality and superior properties. This principle is crucial but challenging to be applied in designing the solid electrolyte interphase (SEI) on lithium metal anodes (LMAs), as it substantially affects Li+ transport from the electrolyte to the anode. Here, an artificial SEI with an ultrahigh fluorine content (as high as 70.12 wt %) can be successfully constructed on the LMA using a high-voltage electrosynthesis strategy. This SEI consists of ultrafine lithium fluoride nanocrystals embedded in a fluorinated organic matrix, exhibiting excellent passivation and mechanical strength. Notably, the organic-inorganic interface demonstrates a high dielectric constant that enables fast Li+ transport throughout the SEI. Consequently, LMA coated with this SEI substantially enhances the cyclability of both half-cells and full cells, even under rigorous conditions. This work demonstrates the potential of rationally designed hybrid materials via a unique electrosynthetic approach for advanced electrochemical systems. [ABSTRACT FROM AUTHOR]

Carbon materials are of great significance in state‐of‐the‐art electrochemical CO2 reduction (ECR) as key components such as electrocatalysts, gas diffusion electrodes, and current collectors. Notably, dimensionalities of carbons and related manipulations play vital roles in boosting ECR performance, e.g., mass/charge transfer dynamics, exposure of active sites, reaction space, product's Faradaic efficiency/selectivity, and durability. Here, recent endeavors in dimensionality engineering toward advanced carbon‐based materials for ECR is first summarized, including pure carbons (e.g., carbon nanotube and graphene) and carbon composites, and highlight the dimensionality‐dependent properties toward ECR performance. Various engineering strategies referring to dimensionality modulation and integration have been summarized, e.g., top‐down, bottom‐up, and soft chemical approaches. Design principles of dimensionality‐varied carbons are elaborated, the impacts of dimensionalities of carbons and related surface chemistry (e.g., functional group, wettability, and electronic structure) on ECR kinetics and product‐targeted mechanisms are also scrutinized. Some insights into how the dimensionality manipulation of carbons elevates performance of carbon‐based materials in mass/charge transfer acceleration, ECR kinetics, and product selectivity are provided. At last, a perspective for challenges and future development of dimensionality‐varied carbon materials is discussed. This review aims at providing guidance for customizable construction of carbon materials with dimensionality dependence toward green and energy‐saving electrosynthesis systems. [ABSTRACT FROM AUTHOR]

A rapid in situ synthesis of electrochromic covalent organic frameworks (EC‐COFs) was proposed by using green electrochemical interface polymerization of N,N,N’,N’‐tetrakis(4‐aminophenyl)‐1,4‐benzenediamine (TPDA) and 2,5‐dihydroxyterephthalaldehyde (DHBD). The synthetized TPDA‐DHBD films exhibit stable polymorphic color variations under different applied potentials, which can be attributed to the redox state changes of bis(triphenylamine) and imine electroactive functional groups within the COFs skeleton. TPDA‐DHBD represents markedly different electrochromisms from red to cyan due to the steric hindrance effect caused by the presence of UO22+, demonstrating the unique tunability of COFs materials. This work offers a new feasible idea for rapid EC‐COFs synthesis and tunable EC‐COFs realization. [ABSTRACT FROM AUTHOR]

The efficient electrosynthesis of hydrogen peroxide (H2O2) via two‐electron oxygen reduction reaction (2e− ORR) in neutral media is undoubtedly a practical route, but the limited comprehension of electrocatalysts has hindered the system advancement. Herein, we present the design of model catalysts comprising mesoporous carbon spheres‐supported Pd nanoparticles for H2O2 electrosynthesis at near‐zero overpotential with approximately 95 % selectivity in a neutral electrolyte. Impressively, the optimized Pd/MCS‐8 electrocatalyst in a flow cell device achieves an exceptional H2O2 yield of 15.77 mol gcatalyst−1 h−1, generating a neutral H2O2 solution with an accumulated concentration of 6.43 wt %, a level sufficiently high for medical disinfection. Finite element simulation and experimental results suggest that mesoporous carbon carriers promote O2 enrichment and localized pH elevation, establishing a favorable microenvironment for 2e− ORR in neutral media. Density functional theory calculations reveal that the robust interaction between Pd nanoparticles and the carbon carriers optimized the adsorption of OOH* at the carbon edge, ensuring high active 2e− process. These findings offer new insights into carbon‐loaded electrocatalysts for efficient 2e− ORR in neutral media, emphasizing the role of carrier engineering in constructing favorable microenvironments and synergizing active sites. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: A novel electrochemical multicomponent cascade reaction of indole‐tethered alkenes with CF3SO2Na and n‐Bu4NI has been developed, which enables the rapid assembly of spiropyrrolidinyl‐oxindoles in good yields. The experimental results and DFT calculations suggest that this reaction proceeds through the oxidation of CF3SO2Na, radical coupling with alkene, spirocyclization, oxidation of sulfinate, iodide substitution, and water coupling. This strategy features mild reaction conditions, easy‐to‐handle reactants, and good chemical yields. This finding not only enriches the research contents of indole‐tethered alkenes but also provides a green strategy for the construction of spiropyrrolidinyl‐oxindoles compared with the existing methodologies. [ABSTRACT FROM AUTHOR]

The time is right for targeted engineering of electroactive microbes for electrobioproduction. Current mixed culture microbial electrosynthesis (MES) and microbial electromethanogenesis are limited to a few low-value products. The product spectrum of MES will greatly benefit from engineered microbial pure cultures, especially with regard to high-value products. To quickly advance MES, standardized, off-the-shelf electrobioreactors are urgently needed. Microbial electrosynthesis (MES) is an emerging technology that couples renewable electricity to microbial production processes. Although advances in MES performance have been driven largely by microbial mixed cultures, we see a great limitation in the diversity, and hence value, of products that can be achieved in undefined mixed cultures. By contrast, metabolic control of pure cultures and genetic engineering could greatly expand the scope of MES, and even of broader electrobiotechnology, to include targeted high-value products. To leverage this potential, we advocate for more efforts and activities to develop engineered electroactive microbes for synthesis, and we highlight the need for a standardized electrobioreactor infrastructure that allows the establishment and engineering of electrobioprocesses with these novel biocatalysts. [ABSTRACT FROM AUTHOR]

Developing pragmatic strategies for accessing functional benzofuran‐2‐ones from 3‐([1,1′‐biphenyl]‐2‐yl)benzofuran remains an enduring challenge. Herein, we have achieved a highly discriminating electrochemical oxidative dearomative spiroannulation of 3‐([1,1′‐biphenyl]‐2‐yl)benzofuran, culminating in the synthesis of 2H‐spiro[benzofuran‐3,9′‐fluoren]‐2‐one derivatives. By harnessing the electrophilic intermediates of benzofuryl radical cations supported by DFT calculations, we attain exceptional regioselectivity while eliminating the need for stoichiometric oxidants. Mechanistic investigations reveal a sequence of events involving the benzofuran radical cation, encompassing the capture of H2O, nucleophilic arene attack, and subsequent deprotonation, ultimately yielding the final benzofuran‐2‐ones. [ABSTRACT FROM AUTHOR]

Electrochemical oxidation of cyclohexane to KA oil, a mixture of cyclohexanone and cyclohexanol, holds great promise for decarbonized chemical manufacturing based on the value of products and the thermodynamic equilibrium potential. However, fundamental understanding of this reaction is extremely limited. For example, even the number of electrons in this reaction has not yet been identified. In this work, we elucidate the mechanism of electrochemical cyclohexane oxidation to KA oil on fluorine-doped tin oxide (FTO), platinum, and glassy carbon anodes. Using three-electrode electroanalysis, isotopic labeling, and concentration studies, we show that electrochemical cyclohexane oxidation to KA oil is similar to its thermochemical analogue in that O2, not water, is the primary oxygen source. The reaction is initiated through the formation of cyclohexyl or hydroxyl radicals, depending on electrode and electrolyte composition. Additionally, crossover from undivided two-electrode cells is found to impact measurements such that cathodic reaction and reactor design may introduce potential artifacts to anodic activity and selectivity. These findings have significant implications for the technological viability of a theoretically promising electrosynthesis process. [ABSTRACT FROM AUTHOR]

This research investigates the impact of laser‐structuring of lead electrodes on the selectivity and production rate of hydrofuroin, a valuable jet fuel precursor derived from furfural (FF). Laser structuring of electrodes led to a slight enhancement in hydrofuroin selectivity, along with an improved production rate, suggesting promising advancements in electrosynthesis methodologies. The addition of acetic acid as an impurity did not significantly affect the selectivity or the production rate. This finding indicates that the catalytic activity of the electrode surface was not diminished by this impurity. Analysis via high‐performance liquid chromatography revealed the presence of two isomers of hydrofuroin, indicating a complex reaction pathway. Combined experimental and molecular dynamics simulations indicated inner sphere adsorption of FF and H+ ions and outer sphere dimerization reaction to form hydrofuroin. These findings offer insights into surface morphology, adsorption, and reaction pathways, guiding future optimization of catalytic systems for sustainable chemical synthesis. [ABSTRACT FROM AUTHOR]

Environmental and energy concerns surrounding the use of fossil fuels are driving an increasingly rapid transition to sustainable and eco‐responsible processes. Electrochemical processes can provide the necessary sustainability and economic roadmap for storing intermittent and renewable electricity by synthesizing, in cogeneration electrolyzers, energy carriers and/or synthetic chemicals (hydrogen, ammonia, etc.) via flagship reduction reactions (hydrogen evolution reaction (HER), nitrogen reduction reaction (NRR), etc.). To balance the electrochemical process, these cathodic processes have long been coupled to the oxygen evolution reaction (OER), which ultimately consumes almost 90% of the energy input. Recent years have witnessed an overwhelming development of anode scenarios based on biomass substrates, because OER cannot be driven below a certain potential threshold, while organics are thermodynamically more favorable. Therefore, paired electrolysis, which refers to cases where electrochemical oxidation and reduction are desired, embraces the electrocatalysis community for the electrolytic production of hydrogen, ammonia, etc. (cathode side), in parallel with value‐added chemicals (anode side), all with a modest electricity input. The trade‐off is selectivity at relevant current densities. This review discusses, the progress, challenges, and potential of biomass‐fueled paired electrosynthesis of valuable chemicals and fuels. Fundamental principles, main biomass solubilization methods, and different scenarios for paired electrosynthesis are presented. [ABSTRACT FROM AUTHOR]

Supercapacitors hold promise for energy storage due to their exceptional power density and fast charge/discharge cycles. However, their performance hinges on the electrode material. Zeolitic imidazolate frameworks (ZIFs) are attractive options due to their tailorable structure and high surface area. But traditional ZIF synthesis relies on toxic solvents derived from fossil fuels, hindering their envisioned environmental benefit. This study explores using bio-derived solvents for a greener and potentially superior approach. The researchers employed anodic electrodeposition to synthesise cobalt-based ZIFs (Co-ZIFs) as supercapacitor electrode materials. Two linkers (2-methylimidazole and benzimidazole) and two bio-derived solvents (CyreneTM and γ-valerolactone (GVL)) were investigated. X-ray diffraction analysis revealed that bio-derived solvents enhanced the crystallinity of Co-ZIFs compared to traditional solvents. Notably, CyreneTM promoted better crystallinity for Co-bIM/Co-mIM structures. The Full Width at Half Maximum (FWHM) analysis suggests CyreneTM promotes Co-bIM/Co-mIM crystallinity (lower FWHM). Co-mIM in CyreneTM exhibits the best crystallinity (FWHM = 0.233) compared to other ZIF samples. Scanning electron microscopy confirmed these findings, showing larger and well-defined crystals for bio-derived solvent-synthesised ZIFs. The choice of solvent significantly impacted the final ZIF structure. While 2-methylimidazole consistently formed ZIF-67 regardless of the solvent, benzimidazole exhibited solvent-dependent behaviour. GVL yielded the highly porous Co-ZIF-12 structure, whereas DMF (N,N-dimethylformamide) and CyreneTM produced the less porous ZIF-9. This work reports the first-ever instance of ZIF-12 synthesis via an electrochemical method, highlighting the crucial interplay between solvent and precursor molecule in determining the final ZIF product. The synthesised binder-free Co-ZIF electrodes were evaluated for supercapacitor performance. The capacitance data revealed GVL as the most effective solvent, followed by DMF and then CyreneTM. This suggests GVL is the preferred choice for this reaction due to its superior performance. The ZIF-12-based electrode exhibits an impressive specific capacitance (Csp) of 44 F g⁻1, significantly higher than those achieved by ZIF-9-Cyrene (1.2 F g⁻1), ZIF-9-DMF (2.5 F g⁻1), ZIF-67-GVL (35 F g⁻1), ZIF-67-Cyrene (6 F g⁻1), and ZIF-67-DMF (16 F g⁻1) at 1 A g−1. This surpasses the Csp of all other ZIFs studied, including high-performing ZIF-67(GVL). ZIF-12(GVL) maintained superior Csp even at higher current densities, demonstrating exceptional rate capability. Among the bio-derived solvents, GVL outperformed CyreneTM. Notably, the Co-bIM in the GVL sample exhibited a ZIF-12-like structure, offering potential advantages due to its larger pores and potentially higher surface area compared to traditional ZIF-67 and ZIF-9 structures. This work presents a significant advancement in Co-ZIF synthesis. By utilising bio-derived solvents, it offers a more sustainable and potentially superior alternative. This paves the way for the eco-friendly production of Co-ZIFs with improved properties for supercapacitors, gas separation, catalysis, and other applications. [ABSTRACT FROM AUTHOR]

BACKGROUND: Surface properties and adsorption performance of carbon materials play a crucial role in the electrochemical two‐electron oxygen reduction to produce H2O2. However, there is still a lack of in‐depth research on commercial carbon blacks in this area. Herein, four typical commercial carbon blacks (Acetylene black (AB), Ketjen black EC 600JD, Vulcan XC 72 and Black Pearls 2000) were used as cathode catalysts to generate H2O2. Surface chemistry and pore structure of electrodes of the four carbon blacks were systematically characterized, and their effects on H2O2 adsorption, electrochemical generation and degradation were investigated. RESULTS: Among the four carbon blacks, AB has the highest content of C–O–C/COOH and CO, which are active groups catalyzing the two‐electron oxygen reduction reaction to generate H2O2. AB has the lowest level of defects and highest degree of graphitization, and AB‐modified graphite felt electrode (AB‐Ele) has the largest average pore diameter, smallest specific surface area and smaller charge transfer resistance. H2O2 production using AB‐Ele is the largest and reaches 567.7 mg L−1 at 180 min under a current density of 5 mA cm−2, and only decreases by 17.6% after 10 repeated uses. CONCLUSION: Overall, rich oxygen‐containing functional groups such as C–O–C, COOH and CO, high degree of graphitization, suitable surface area and porosity as well as weak H2O2 adsorption performance are beneficial for the two‐electron oxygen reduction reaction to generate H2O2. AB‐modified graphite felt electrode exhibits good catalytic activity and reusability in H2O2 electrosynthesis, demonstrating promising application prospects. © 2024 Society of Chemical Industry (SCI). [ABSTRACT FROM AUTHOR]

The electrochemical nitrate reduction reaction (NO3RR) is able to convert nitrate (NO3−) into reusable ammonia (NH3), offering a green treatment and resource utilization strategy of nitrate wastewater and ammonia synthesis. The conversion of NO3− to NH3 undergoes water dissociation to generate active hydrogen atoms and nitrogen‐containing intermediates hydrogenation tandemly. The two relay processes compete for the same active sites, especially under pH‐neutral condition, resulting in the suboptimal efficiency and selectivity in the electrosynthesis of NH3 from NO3−. Herein, we constructed a Cu1‐Fe dual‐site catalyst by anchoring Cu single atoms on amorphous iron oxide shell of nanoscale zero‐valent iron (nZVI) for the electrochemical NO3RR, achieving an impressive NO3− removal efficiency of 94.8 % and NH3 selectivity of 99.2 % under neutral pH and nitrate concentration of 50 mg L−1 NO3−−N conditions, greatly surpassing the performance of nZVI counterpart. This superior performance can be attributed to the synergistic effect of enhanced NO3− adsorption on Fe sites and strengthened water activation on single‐atom Cu sites, decreasing the energy barrier for the rate‐determining step of *NO‐to‐*NOH. This work develops a novel strategy of fabricating dual‐site catalysts to enhance the electrosynthesis of NH3 from NO3−, and presents an environmentally sustainable approach for neutral nitrate wastewater treatment. [ABSTRACT FROM AUTHOR]

Aryl radicals play a pivotal role as reactive intermediates in chemical synthesis, commonly arising from aryl halides and aryl diazo compounds. Expanding the repertoire of sources for aryl radical generation to include abundant and stable organoboron reagents would significantly advance radical chemistry and broaden their reactivity profile. While traditional approaches utilize stoichiometric oxidants or photocatalysis to generate aryl radicals from these reagents, electrochemical conditions have been largely underexplored. Through rigorous mechanistic investigations, we identified fundamental challenges hindering aryl radical generation. In addition to the high oxidation potentials of aromatic organoboron compounds, electrode passivation through radical grafting, homocoupling of aryl radicals, and decomposition issues were identified. We demonstrate that pulsed electrosynthesis enables selective and efficient aryl radical generation by mitigating the fundamental challenges. Our discoveries facilitated the development of the first electrochemical conversion of aryl potassium trifluoroborate salts into aryl C−P bonds. This sustainable and straightforward oxidative electrochemical approach exhibited a broad substrate scope, accommodating various heterocycles and aryl chlorides, typical substrates in transition‐metal catalyzed cross‐coupling reactions. Furthermore, we extended this methodology to form aryl C−Se, C−Te, and C−S bonds, showcasing its versatility and potential in bond formation processes. [ABSTRACT FROM AUTHOR]

The electrochemical C‐N coupling process, facilitating the production of organic nitrogen substances (such as urea, methylamine, formamide, and ethylamine) via the simultaneous reduction of carbon dioxide (CO2) and small nitrogen‐based substances, stands at the forefront of advancing carbon neutrality and the artificial nitrogen cycle. This method has garnered substantial interest due to its potential economic and environmental benefits. Although considerable progress has been achieved in this emerging field, it still faces challenges, including slow reactant adsorption, competing side reactions, and complex multi‐step pathways, resulting in low yields and selectivity. Strategically designing and developing low‐cost and exceptionally performant catalysts is crucial for cost‐effective and precise electrochemical C─N bonding. This article offers an in‐depth review of the electrosynthesis of valuable organic nitrogen compounds at ambient conditions from earth‐abundant resources/wastes, such as CO2 and small nitrogenous molecules (nitrogen: N2, nitrite: NO2−, nitrate: NO3−, ammonia: NH3, etc.), via electrochemical C─N bond formation reactions, especially using carbon‐based catalysts. The relevant electrochemical C─N bond formation mechanisms, the design principles of advanced carbon‐based electrocatalysts, and the impact of different electrolyser designs are discussed, along with the present obstacles and upcoming prospects in this dynamic field. [ABSTRACT FROM AUTHOR]

In this study, a new green method was developed for the synthesis of bis(indolyl)methane derivatives using electrochemical bisarylation reaction in deep eutectic solvents as a green alternative to traditional solvents and electrolytes. The effects of varying time, current, type of solvent and material of electrodes were all studied. The optimum reaction conditions involved the use of ethylene glycol/choline chloride with a ratio of 2:1 at 80 °C for 45 min. Graphite and platinum were used as cathode and anode, respectively. The newly developed method offered many advantages such as using mild reaction conditions, short reaction time and affording high product yields with a wide range of substituted aromatic aldehydes bearing electron donating or electron withdrawing substituents. In addition, the electrochemical method proved to be more effective than heating in deep eutectic solvents and afforded higher yields of products in shorter reaction time. The mechanism of the electrochemical reaction was proposed and confirmed using the cyclic voltammetry study. [ABSTRACT FROM AUTHOR]

Herein, a microporous organic–inorganic hybrid, vanadium phosphonate (VPn) material has been developed. With the combined advantages of the periodic organic–inorganic skeleton, a regular microporous channel with a crystalline pore wall, and good surface area, VPn displays electrocatalytic NRR activity with a selective NH3 yield (11.84 μg h−1 mgcat−1), faradaic efficiency of 26.29% at −0.6 V and high stability up to 15 h. The isotopic labeling experiment also verifies the electrosynthesis of NH3 both qualitatively and quantitatively. The theoretical simulation reveals that the associative distal route serves as the most favourable pathway during the NRR, with the first protonation step of *N2 leading to *NNH as the potential determining step. [ABSTRACT FROM AUTHOR]

Acidic H2O2 synthesis through electrocatalytic 2e− oxygen reduction presents a sustainable alternative to the energy‐intensive anthraquinone oxidation technology. Nevertheless, acidic H2O2 electrosynthesis suffers from low H2O2 Faradaic efficiencies primarily due to the competing reactions of 4e− oxygen reduction to H2O and hydrogen evolution in environments with high H+ concentrations. Here, we demonstrate the significant effect of alkali metal cations, acting as competing ions with H+, in promoting acidic H2O2 electrosynthesis at industrial‐level currents, resulting in an effective current densities of 50–421 mA cm−2 with 84–100 % Faradaic efficiency and a production rate of 856–7842 μmol cm−2 h−1 that far exceeds the performance observed in pure acidic electrolytes or low‐current electrolysis. Finite‐element simulations indicate that high interfacial pH near the electrode surface formed at high currents is crucial for activating the promotional effect of K+. In situ attenuated total reflection Fourier transform infrared spectroscopy and ab initio molecular dynamics simulations reveal the central role of alkali metal cations in stabilizing the key *OOH intermediate to suppress 4e− oxygen reduction through interacting with coordinated H2O. [ABSTRACT FROM AUTHOR]

Asymmetric electrosynthesis provides an efficient and controllable route for chiral synthesis. In comparison to traditional symmetric synthesis methods, asymmetric electrosynthesis typically operates under milder conditions, reducing waste generation and energy consumption. This aligns with the current trend in green chemistry, contributing to the development of environmentally friendly synthetic pathways. Apart from reactions initiated with chiral substrates, introducing appropriate chiral factors during the electrochemical process is crucial. In this context, chiral electrodes have garnered significant attention due to their advantages such as high catalytic activity, enantioselectivity, and reusability. This concept aims to introduce the preparation of three main types of chiral electrodes over the past decade, including chiral modified electrodes, chiral immobilized electrodes and chiral imprinted electrodes, and their applications in asymmetric electrosynthesis. The article provides insights into the current state of the field and outlines prospects for future research. [ABSTRACT FROM AUTHOR]