Conductive Polypropylene Additive Manufacturing Feedstock: Application to Aqueous Electroanalysis and Unlocking Nonaqueous Electrochemistry and Electrosynthesis.

Additive manufacturing electrochemistry is an ever-expanding field; however, it is limited to aqueous environments due to the conductive filaments currently available. Herein, the production of a conductive poly(propylene) filament, which unlocks the door to organic electrochemistry and electrosynthesis, is reported. A filament with 40 wt % carbon black possessed enhanced thermal stability, excellent low-temperature flexibility, and high conductivity. The filament produced highly reproducible additive manufactured electrodes that were electrochemically characterized, showing a k0 of 2.00 ± 0.04 × 10-3 cm s-1. This material was then applied to three separate electrochemical applications. First, the electroanalytical sensing of colchicine within environmental waters, where a limit of detection of 10 nM was achieved before being applied to tap, bottled, and river water. Second, the electrodes were stable in organic solvents for 100 cyclic voltammograms and 15 days. Finally, these were applied toward an electrosynthetic reaction of chlorpromazine, where the electrodes were stable for 24-h experiments, outperforming a glassy carbon electrode, and were able to be reused while maintaining a good electrochemical performance. This material can revolutionize the field of additive manufacturing electrochemistry and expand research into a variety of new fields.

Low electric current in a bioelectrochemical system facilitates ethanol production from CO using CO-enriched mixed culture.

Fossil resources must be replaced by renewable resources in production systems to mitigate green-house gas emissions and combat climate change. Electro-fermentation utilizes a bioelectrochemical system (BES) to valorize industrial and municipal waste. Current electro-fermentation research is mainly focused on microbial electrosynthesis using CO2 for producing commodity chemicals and replacing petroleum-based infrastructures. However, slow production rates and low titers of metabolites during CO2-based microbial electrosynthesis impede its implementation to the real application in the near future. On the other hand, CO is a highly reactive gas and an abundant feedstock discharged from fossil fuel-based industry. Here, we investigated CO and CO2 electro-fermentation, using a CO-enriched culture. Fresh cow fecal waste was enriched under an atmosphere of 50% CO and 20% CO2 in N2 using serial cultivation. The CO-enriched culture was dominated by Clostridium autoethanogenum (≥89%) and showed electro-activity in a BES reactor with CO2 sparging. When 50% CO was included in the 20% CO2 gas with 10 mA applied current, acetate and ethanol were produced up to 12.9 ± 2.7 mM and 2.7 ± 1.1 mM, respectively. The coulombic efficiency was estimated to 148% ± 8% without an electron mediator. At 25 mA, the culture showed faster initial growth and acetate production but no ethanol production, and only at 86% ± 4% coulombic efficiency. The maximum optical density (OD) of 10 mA and 25 mA reactors were 0.29 ± 0.07 and 0.41 ± 0.03, respectively, whereas it was 0.77 ± 0.19 without electric current. These results show that CO electro-fermentation at low current can be an alternative way of valorizing industrial waste gas using a bioelectrochemical system.

A Universal Synthesis of Single-Atom Catalysts via Operando Bond Formation Driven by Electricity.

Single-atom catalysts (SACs), featuring highly uniform active sites, tunable coordination environments, and synergistic effects with support, have emerged as one of the most efficient catalysts for various reactions, particularly for electrochemical CO2 reduction (ECR). However, the scalability of SACs is restricted due to the limited choice of available support and problems that emerge when preparing SACs by thermal deposition. Here, an in situ reconstruction method for preparing SACs is developed with a variety of atomic sites, including nickel, cadmium, cobalt, and magnesium. Driven by electricity, different oxygen-containing metal precursors, such as MOF-74 and metal oxides, are directly atomized onto nitrogen-doped carbon (NC) supports, yielding SACs with variable metal active sites and coordination structures. The electrochemical force facilitates the in situ generation of bonds between the metal and the supports without the need for additional complex steps. A series of MNxOy (M denotes metal) SACs on NC have been synthesized and utilized for ECR. Among these, NiNxOy SACs using Ni-MOF-74 as a metal precursor exhibit excellent ECR performance. This universal and general SAC synthesis strategy at room temperature is simpler than most reported synthesis methods to date, providing practical guidance for the design of the next generation of high-performance SACs.

Accelerated Proton-Coupled Electron Transfer via Engineering Palladium Sub-Nanoclusters for Scalable Electrosynthesis of Hydrogen Peroxide.

Electrosynthesis of H2O2 from oxygen reduction reaction via a two-electron pathway is vital as an alternative for the energy-intensive anthraquinone process. However, this process is largely hindered in neutral and alkaline conditions due to sluggish kinetics associated with the transformation of intermediate O2* into OOH* via proton-coupled electron transfer sourced from slow water dissociation. Herein, we developed Pd sub-nanoclusters on the nickel ditelluride nanosheets (Pd SNCs/NiTe2) to enhance the performance of H2O2 electrosynthesis. The newly-developed Pd SNCs/NiTe2 exhibited a H2O2 selectivity of as high as 99% and a positive shift of onset potential up to 0.81 V. Combined theoretical calculations and experimental studies (e.g., X-ray absorption and attenuated total reflectance-Fourier transform infrared spectra measurements) revealed that the Pd sub-nanoclusters supported by NiTe2 nanosheets efficiently reduced the energy barrier of water dissociation to generate more protons, facilitating the proton feeding kinetics. When used in a flow cell, Pd SNCs/NiTe2 cathode efficiently produced H2O2 with a maximum yield rate of 1.75 mmol h-1 cm-2 and current efficiency of 95% at 100 mA cm-2. Further, an accumulated H2O2 concentration of 1.43 mol L-1 was reached after 10 hours of continuous electrolysis, showing the potential for practical H2O2 electrosynthesis.

Boosting Electroreduction of Nitrate and CO2 to Urea on a Tandem Fe1/MoS2 Catalyst.

Urea electrosynthesis by coelectrolysis of NO3- and CO2 (UENC) holds enormous promise for sustainable urea production, while the efficient UENC process relies on the rational design of high-performance catalysts to facilitate the electrocatalytic C-N coupling efficiency and the hydrogenation reaction process. Herein, Fe single atoms supported on MoS2 (Fe1/MoS2) are developed as a highly effective and robust catalyst for UENC. Theoretical calculations and operando spectroscopic measurements reveal a tandem catalysis mechanism of the Fe1-S3 motif and MoS2-edge to jointly promote the UENC process, where the Fe1-S3 motif drives the early C-N coupling and subsequent *CO2NO2-to-*CO2NH2 step. The generated *CO2NH2 is then migrated from the Fe1-S3 motif to the nearby MoS2-edge, which facilitates the *CO2NH2 → *COOHNH2 step for urea formation. Noticeably, Fe1/MoS2 assembled in a flow cell reaches a maximum urea Faraday efficiency of 54.98% with a corresponding urea yield rate of 18.98 mmol h-1 g-1, performing at the top level among all of the UENC catalysts reported to date.

Hypochlorous acid electrosynthesis and service life assessment of a Ti|Ti-Ru-Ir-oxides anode assembled in a flow electrolyzer: Understanding the influence of the concurrent O2 bubbling flow.

This paper addresses the influence of bubbling flow and service life of the Ti|Ti-Ru-Ir-oxides anode during the electrosynthesis of HClO in a laboratory-scale filter-press-type electrolyzer. The electrolyzer was assembled in a flow plant in recirculation mode. Polarization curves in rotating disk electrode (RDE) revealed the coexistence of the oxygen evolution reaction (OER) during HClO electrosynthesis in diluted chloride solutions (containing 35 mM NaCl at pH 3). CFD simulations of the two-phase (O2-H2O) flow were obtained by solving simultaneously the Navier-Stokes and charge conservation equations using a finite element method code. The O2-H2O simulations show the efficient gas release in the electrolyzer provoked by the continuous phase (H2O) inertia and the well-engineered cell design. The moderated O2 dispersion caused a quasi-homogeneous current distribution along the anode. However, the current efficiency during HClO electrosynthesis gave values of ∼32% provoked by the OER on the anode. The HClO accumulations (from 3.02 to 6.64 mM) showed excellent agreement with CFD simulations. The accelerated life tests revealed that the Ti | Ti-Ru-Ir-oxides anode has a lifetime of at least 26 years during the HClO electrosynthesis in diluted chloride solutions.

Nitrogen-doped carbon dots boost microbial electrosynthesis via efficient extracellular electron uptake of acetogens.

This study investigated the molecular mechanism behind the highly efficient performance of nitrogen-doped carbon dots (NCDs)-assisted microbial electrosynthesis systems (MESs). The impact of NCDs (C:N precursor = 1:0.5-1:3) on acetogens was examined in the biocathode. The highest electrocatalytic performance was observed with NCDs1:1. The maximum acetate production rate of 1.9 ± 0.1 mM d-1 was achieved in NCDs1:1-modified MESs, which was 26.7-216.7 % higher than other MESs (0.6-1.5 mM d-1). With NCDs1:1 modified, the biocathode exhibited a 129.3-186.8 % increase in the abundance of Sporomusa, and 38.5-104.6 % increase in cytochrome expression (cydAB, cybH). Transcriptome confirmed that cytochromes played a crucial role in the extracellular electron uptake (EEU) of NCDs1:1-modified Sporomusa. NCDs1:1 enhanced EEU efficiency, thereby increasing the two H+-pumping steps and accelerating microbial CO2 fixation. These results provide valuable insights into increasing CO2 fixation by maximizing EEU efficiency in acetogens.

Regulating RuxMoy Nanoalloys Anchored on Porous Nitrogen-Doped Carbon via Domain-Confined Etching Strategy for Neutral Efficient Ammonia Electrosynthesis.

Neutral electrochemical nitrate (NO3-) reduction to ammonia involves sluggish and complex kinetics, so developing efficient electrocatalysts at low potential remains challenging. Here, we report a domain-confined etching strategy to construct RuxMoy nanoalloys on porous nitrogen-doped carbon by optimizing the Ru-to-Mo ratio, achieving efficient neutral NH3 electrosynthesis. Combining in situ spectroscopy and theoretical simulations demonstrated a rational synergic effect between Ru and Mo in nanoalloys that reinforces *H adsorption and lowers the energy barrier of NO3- hydrodeoxygenation for NH3 production. The resultant Ru5Mo5-NC surpasses 92.8% for NH3 selectivity at the potential range from -0.25 to -0.45 V vs RHE under neutral electrolyte, particularly achieving a high NH3 selectivity of 98.3% and a corresponding yield rate of 1.3 mg h-1 mgcat-1 at -0.4 V vs RHE. This work provides a synergic strategy that sheds light on a new avenue for developing efficient multicomponent heterogeneous catalysts.

High-Density Atomically Dispersed Metals Activate Adjacent Nitrogen/Carbon Sites for Efficient Ammonia Electrosynthesis from Nitrate.

While electrocatalytic reduction of nitrate to ammonia presents a sustainable solution for addressing both the environmental and energy issues within the nitrogen cycle, it remains a great challenge to achieve high selectivity and activity due to undesired side reactions and sluggish reaction kinetics. Here, we fabricate a series of metal-N-C catalysts that feature hierarchically ordered porous structure and high-density atomically dispersed metals (HD M1/PNC). Specifically, the as-prepared HD Fe1/PNC catalyst achieves an ammonia production rate of 21.55 mol gcat-1 h-1 that is at least 1 order of magnitude enhancement compared with that of the reported metal-N-C catalysts, while maintaining a 92.5% Faradaic efficiency when run at 500 mA cm-2 for 300 h. In addition to abundant active sites, such high performance benefits from the fact that the high-density Fe can more significantly activate the adjacent N/C sites through charge redistribution for improved water adsorption/dissociation, providing sufficient active hydrogen to Fe sites for nitrate ammoniation, compared with the low-density counterpart. This finding deepens the understanding of high-density metal-N-C materials at the atomic scale and may further be used for designing other catalysts.

Progress of Metal Chalcogenides as Catalysts for Efficient Electrosynthesis of Hydrogen Peroxide.

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.

Rectifying Heterointerface Facilitated C-N Coupling Dynamics Enables Efficient Urea Electrosynthesis Under Ultralow Potentials.

Electrocatalytic C-N coupling for urea synthesis from carbon dioxide (CO2) and nitrate (NO3-) offers a sustainable alternative to the traditional Bosch-Meiser method. However, the complexity of intermediates in co-reduction hampers simultaneous improvement in urea yield and Faradaic efficiency (FE). Herein, we developed a Cu/Cu2O Mott-Schottky catalyst with nanoscale rectifying heterointerfaces through precise controllable in-situ electroreduction of Cu2O nanowires, achieving notable FE (32.6-47.0%) and substantial yields (6.08-30.4 µmol h-1 cm-2) across a broad range of ultralow applied potentials (0 to -0.3 V vs. RHE). Operando synchrotron radiation-Fourier transform infrared spectroscopy (SR-FTIR) confirmed the formation of *CO intermediates and C-N bonds, subsequently density functional theory (DFT) calculations deciphered that the Cu/Cu2O rectifying heterointerface modulated *CO adsorption, significantly enhancing subsequent C-N coupling dynamics between *CO and *NOH intermediates. This work not only provides a groundbreaking and advanced pathway for C-N coupling, but also offers deep insights into copper-based heterointerface catalysts for urea synthesis.

Stabilizing Hydrogen Radicals in Two-Dimensional Cobalt-Copper Mesoporous Nanoplates for Complete Nitrate Reduction Electrocatalysis to Ammonia.

Ambient electrochemical reduction of waste nitrate (NO3-) represents an alternative green route for sustainable ammonia (NH3) electrosynthesis in water. Despites some encouraged achievements, sluggish eight electron and nine proton reduction routes that involve multi-step hydrogenation pathways have severely hindered their NH3 Faradaic efficiency (FENH3) and yield rate. Herein, we develop a robust two-dimensional mesoporous cobalt-copper (meso-CoCu) nanoplate electrocatalyst that delivers excellent performance of complete NO3- reduction reaction (NO3RR), including superior FENH3 of 98.8%, high NH3 yield rate of 3.39 mol h-1 g-1 and energy efficiency of 49.8%, and good cycling stability. Mechanism investigations unveil that active hydrogen (*H) radicals produced from water splitting on Co sites spillover to adjacent Cu sites and further stabilize within confined mesopores, which kinetically promote its coupling hydrogenation reactions of nitrogen intermediates and thus facilitate complete NO3RR for favorable NH3 electrosynthesis. Moreover, meso-CoCu nanoplates perform well as a bifunctional electrocatalyst in the two-electrode coupling system that concurrently synthesizes NH3 from NO3- at cathode and 2,5-furanedicarboxylic acid from 5-hydroxymethylfurfural at anode. This work in stabilizing *H radicals in mesoporous microenvironment provides some insights applied to various hydrogenation reactions for selective electrosynthesis of highly value-added chemicals in water.

Atomic Defects Engineering Boosts Urea Synthesis toward Carbon Dioxide and Nitrate Coelectroreduction.

The atomic defect engineering could feasibly decorate the chemical behaviors of reaction intermediates to regulate catalytic performance. Herein, we created oxygen vacancies on the surface of In(OH)3 nanobelts for efficient urea electrosynthesis. When the oxygen vacancies were constructed on the surface of the In(OH)3 nanobelts, the faradaic efficiency for urea reached 80.1%, which is 2.9 times higher than that (20.7%) of the pristine In(OH)3 nanobelts. At -0.8 V versus reversible hydrogen electrode, In(OH)3 nanobelts with abundant oxygen vacancies exhibited partial current density for urea of -18.8 mA cm-2. Such a value represents the highest activity for urea electrosynthesis among recent reports. Density functional theory calculations suggested that the unsaturated In sites adjacent to oxygen defects helped to optimize the adsorbed configurations of key intermediates, promoting both the C-N coupling and the activation of the adsorbed CO2NH2 intermediate. In-situ spectroscopy measurements further validated the promotional effect of the oxygen vacancies on urea electrosynthesis.

Electrochemical allylations in a deep eutectic solvent.

Electrosynthesis is a technique that is attracting increased attention and has many appealing features, particularly its potential greenness. At the same time, electrosynthesis requires a solvent and a supporting electrolyte in order for current to pass through the reaction. These are effectively consumable reagents unless a convenient means of recycling can be developed. As part of our interest in unusual solvents and electrochemistry, we explored the application of simple, inexpensive, and recyclable deep eutectic solvents to the allylation of carbonyls. While several sets of conditions were developed, the goal of avoiding stoichiometric amounts of metal has proven elusive. Still, a deep eutectic solvent can be used to plate out and thus recover the metal used, offering an interesting new option for electrochemical allylations.

A Strongly Coupled Metal/Hydroxide Heterostructure Cascades Carbon Dioxide and Nitrate Reduction Reactions toward Efficient Urea Electrosynthesis.

The direct coupling of nitrate ions and carbon dioxide for urea synthesis presents an appealing alternative to the Bosch-Meiser process in industry. The simultaneous activation of carbon dioxide and nitrate, however, as well as efficient C-N coupling on single active site, poses significant challenges. Here, we propose a novel metal/hydroxide heterostructure strategy based on synthesizing an Ag-CuNi(OH)2 composite to cascade carbon dioxide and nitrate reduction reactions for urea electrosynthesis. The strongly coupled metal/hydroxide heterostructure interface integrates two distinct sites for carbon dioxide and nitrate activation, and facilitates the coupling of *CO (on silver, where * denotes an active site) and *NH2 (on hydroxide) for urea formation. Moreover, the strongly coupled interface optimizes the water splitting process and facilitates the supply of active hydrogen atoms, thereby expediting the deoxyreduction processes essential for urea formation. Consequently, our Ag-CuNi(OH)2 composite delivers a high urea yield rate of 25.6 mmol gcat.-1 h-1 and high urea Faradaic efficiency of 46.1%, as well as excellent cycling stability. This work provides new insights into the design of dual-site catalysts for C-N coupling, considering their role on the interface.

Electrochemical Hydrodimerization of Lignocellulose-derived Carbonyls in Aqueous Electrolytes for Biobased Polymer and Long-chained Synfuel Production: A Review.

The transformation from fossil resources, crude oil and natural gas to biomass-derived feedstocks is an urgent and major challenge for the chemical industry. The valorization of lignocellulose as renewable resource is a promising pathway offering access to a wide range of platform chemicals, such as vanillin, furfural and 5-HMF. The subsequent conversion of such platform chemicals is one crucial step in the value-added chain. The electrochemical hydrodimerization (EHD) is a sustainable tool for C-C coupling of these chemicals to their corresponding hydrodimers hydrovanilloin, hydrofuroin and 5,5´-bis(hydroxymethyl)hydrofuroin (BHH). This review covers the current state of art concerning the mechanism of the electrochemical reduction of biobased aldehydes and studies targeting the electrochemical production of these hydrodimers in aqueous media. Moreover, the subsequent conversion of these hydrodimers to valuable additives, polymers and long carbon chain synfuels will be summarized offering a broad scope for their application in the chemical industry.

In Situ Electrochemical Interfacial Polymerization for Covalent Organic Frameworks with Tunable Electrochromism.

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 UO2 2+, demonstrating the unique tunability of COFs materials. This work offers a new feasible idea for rapid EC-COFs synthesis and tunable EC-COFs realization.

Dynamic Control of Asymmetric Charge Distribution for Electrocatalytic Urea Synthesis.

Constructing dual catalytic sites with charge density differences is an efficient way to promote urea electrosynthesis from parallel NO 3 - ${\mathrm{NO}}_3^ - $ and CO2 reduction yet still challenging in static system. Herein, a dynamic system is constructed by precisely controlling the asymmetric charge density distribution in an Au-doped coplanar Cu7 clusters-based 3D framework catalyst (Au@cpCu7CF). In Au@cpCu7CF, the redistributed charge between Au and Cu atoms changed periodically with the application of pulse potentials switching between -0.2 and -0.6 V and greatly facilitated the electrosynthesis of urea. Compared with the static condition of pristine cpCu7CF (FEurea = 5.10%), the FEurea of Au@cpCu7CF under pulsed potentials is up to 55.53%. Theoretical calculations demonstrated that the high potential of -0.6 V improved the adsorption of *HNO2 and *NH2 on Au atoms and inhibited the reaction pathways of by-products. While at the low potential of -0.2 V, the charge distribution between Au and Cu atomic sites facilitated the thermodynamic C-N coupling step. This work demonstrated the important role of asymmetric charge distribution under dynamic regulation for urea electrosynthesis, providing a new inspiration for precise control of electrocatalysis.

Metal Atom-Support Interaction in Single Atom Catalysts toward Hydrogen Peroxide Electrosynthesis.

Single metal atom catalysts (SACs) have garnered considerable attention as promising agents for catalyzing important industrial reactions, particularly the electrochemical synthesis of hydrogen peroxide (H2O2) through the two-electron oxygen reduction reaction (ORR). Within this field, the metal atom-support interaction (MASI) assumes a decisive role, profoundly influencing the catalytic activity and selectivity exhibited by SACs, and triggers a decade-long surge dedicated to unraveling the modulation of MASI as a means to enhance the catalytic performance of SACs. In this comprehensive review, we present a systematic summary and categorization of recent advancements pertaining to MASI modulation for achieving efficient electrochemical H2O2 synthesis. We start by introducing the fundamental concept of the MASI, followed by a detailed and comprehensive analysis of the correlation between the MASI and catalytic performance. We describe how this knowledge can be harnessed to design SACs with optimized MASI to increase the efficiency of H2O2 electrosynthesis. Finally, we distill the challenges that lay ahead in this field and provide a forward-looking perspective on the future research directions that can be pursued.

Single-Atom Rh1 Alloyed Co for Urea Electrosynthesis from CO2 and NO3.

Single-atom Rh1 alloyed Co (Rh1Co) is explored as an efficient catalyst for urea electrosynthesis via coelectrolysis of CO2 and NO3- (UECN). Theoretical calculations and in situ spectroscopic measurements unravel the synergetic effect of Co and Rh1 in promoting the UECN process, where the Rh1 site activates NO3- to form *NH2, while the Co site activates CO2 to form *CO. The formed *CO then desorbs from the Co site and transfers to the Rh1 site, followed by continuous C-N coupling with *NH2 formed on the Rh1 site to synthesize urea. Remarkably, Rh1Co assembled in a flow cell delivers the exceptional urea yield rate of 24.9 mmol h-1 g-1 and Faradaic efficiency of 51.1%, outperforming most previously reported UECN catalysts.