Electrochemical Decomposition Research Articles

Promoted Reaction Reversibility by Dual-Effect 15-Crown-5 Ether Additive for High-Performance Li-O2 Batteries.

The practical application of lithium-oxygen batteries (LOBs) with ultrahigh theoretical energy density faces the problems of poor kinetics and deficient reversibility. The electrolyte is of vital significance to the electrochemical stability and reaction pathway of LOBs due to the formation of soluble products. Here, a 15-crown-5 ether (15C5) is employed to regulate the solvation structure of Li+ and manipulate the reaction mechanism through regulating the binding ability toward Li+. The promoted dissociation of LiNO3 by 15C5 increases the catalytical active anions in the electrolyte and stabilizes the Li-containing reduced oxygen species to promote the solution pathway of discharge product growth. Besides, 15C5 also facilitates the kinetics of the electrochemical decomposition of Li2O2 and prolongs the cycle life to 178 cycles. This work inspires a novel approach to improve the battery performance through electrolyte component design.

Bimetallic electrocatalysts based on polyoxometalate for hydrogen evolution and urea oxidation reaction

Electrochemical water decomposition is an efficient and environmentally friendly method for producing hydrogen. Because of the high voltage required for water electrolysis, using anodic urea oxidation process (UOR) to replace the oxygen evolution reaction can significantly cut energy usage. In this paper, hydrogen evolution reaction (HER) and urea oxidation process (UOR) electrocatalysts were synthesized by one-step carbonization using giant polyoxomolybdate cluster Mo132 and triethylamine at different temperatures. Ni/MoN@NC obtained at 800 °C shows good HER effect in the acidic electrolyte, an overpotential of 94 mV can provide the current density of 10 mA cm−2. Ni/NiO@NC obtained by calcination at 400 °C exhibits good UOR performance, in which the potential is 1.41 V when the current density is 10 mA cm−2. Efficient HER performance depends on the synergy of Ni and MoN. The highly efficient UOR is derived from the hierarchical structure of Ni and NiO. Furthermore, the porous structure also enhances the full contact between electrolyte and active sites, the catalytic performance of the catalyst was improved benefit to improve the catalytic activity. This work affords a general approach to simply synthesize efficient hydrogen producing materials for HER and small molecules oxidation fields.

Core-Shell CoS2@MoS2 with Hollow Heterostructure as an Efficient Electrocatalyst for Boosting Oxygen Evolution Reaction.

It is imperative to develop an efficient catalyst to reduce the energy barrier of electrochemical water decomposition. In this study, a well-designed electrocatalyst featuring a core-shell structure was synthesized with cobalt sulfides as the core and molybdenum disulfide nanosheets as the shell. The core-shell structure can prevent the agglomeration of MoS2, expose more active sites, and facilitate electrolyte ion diffusion. A CoS2/MoS2 heterostructure is formed between CoS2 and MoS2 through the chemical interaction, and the surface chemistry is adjusted. Due to the morphological merits and the formation of the CoS2/MoS2 heterostructure, CoS2@MoS2 exhibits excellent electrocatalytic performance during the oxygen evolution reaction (OER) process in an alkaline electrolyte. To reach the current density of 10 mA cm-2, only 254 mV of overpotential is required for CoS2@MoS2, which is smaller than that of pristine CoS2 and MoS2. Meanwhile, the small Tafel slope (86.9 mV dec-1) and low charge transfer resistance (47 Ω) imply the fast dynamic mechanism of CoS2@MoS2. As further confirmed by cyclic voltammetry curves for 1000 cycles and the CA test for 10 h, CoS2@MoS2 shows exceptional catalytic stability. This work gives a guideline for constructing the core-shell heterostructure as an efficient catalyst for oxygen evolution reaction.

Regulation of electron density redistribution for efficient alkaline hydrogen evolution reaction and overall water splitting

The rational design of morphology and heterogeneous interfaces for non-precious metal electrocatalysts is crucial in electrochemical water decomposition. In this paper, a bifunctional electrocatalyst (Ni/NiFe LDH), which coupling nickel with nickel–iron layer double hydroxide (NiFe LDH), is synthesized on carbon cloth. At current density of 10 mA cm−2, the Ni/NiFe LDH exhibits a low hydrogen evolution reaction (HER) overpotential of only 36 mV due to the accelerated electrolyte penetration, which is caused by superhydrophilic interface. Moreover, an alkaline electrolyzer is formed and provide a current density of 10 mA cm−2 with a voltage of only 1.49 V. It is confirmed by the density functional theory (DFT) that electron from the Ni layer is transferred to NiFe LDH layer, redistributing the local electron density around the heterogeneous phase interface. Thus, the Gibbs free energy for hydrogen adsorption is optimized. This work provides a promising strategy for the rational regulation of electrons at heterogeneous interfaces and the synthesis of flexible electrocatalysts.

Managing PFAS exhausted Ion-exchange resins through effective regeneration/electrochemical process

This study proposes an integrated approach that combines ion-exchange (IX) and electrochemical technologies to tackle problems associated with PFAS contamination. Our investigation centers on evaluating the recovery and efficiency of IX/electrochemical systems in the presence of five different salts, spanning dosages from 0.1 % to 8 %. The outcomes reveal a slight superiority for NaCl within the regeneration system, with sulfate and bicarbonate also showing comparable efficacy. Notably, the introduction of chloride ion (Cl−) into the electrochemical system results in substantial generation of undesirable chlorate (ClO3−) and perchlorate (ClO4−) by-products, accounting for ∼18 % and ∼81 % of the consumed Cl−, respectively. Several agents, including H2O2, KI, and Na2S2O3, exhibited effective mitigation of ClO3− and ClO4− formation. However, only H2O2 demonstrated a favorable influence on the degradation and defluorination of PFOA. The addition of 0.8 M H2O2 resulted in the near-complete removal of ClO3− and ClO4−, accompanied by 1.3 and 2.2-fold enhancements in the degradation and defluorination of PFOA, respectively. Furthermore, a comparative analysis of different salts in the electrochemical system reveals that Cl− and OH− ions exhibit slower performance, possibly due to competitive interactions with PFOA on the anode's reactive sites. In contrast, sulfate and bicarbonate salts consistently demonstrate robust decomposition efficiencies. Despite the notable enhancement in IX regeneration efficacy facilitated by the presence of methanol, particularly for PFAS-specific resins, this enhancement comes at the cost of reduced electrochemical decomposition of all PFAS. The average decay rate ratio of all PFAS in the presence of 50 % methanol, compared to its absence, falls within the range of 0.11–0.39. In conclusion, the use of 1 % Na2SO4 salt stands out as a favorable option for the integrated IX/electrochemical process. This choice not only eliminates the need to introduce an additional chemical (e.g., H2O2) into the wastewater stream, but also ensures both satisfactory regeneration recovery and efficiency in the decomposition process through electrochemical treatment.

Application of Na2CO3 as a Sacrificial Electrode Additive in Na‐ion Batteries to Compensate for the Sodium Deficiency in Na2/3[Fe1/2Mn1/2]O2

AbstractOwing to their high discharge capacities, P2‐type transition metal layered oxides have attracted attention for use as positive electrode materials in Na‐ion batteries. However, owing to the Na‐deficient compositions of these oxides, additional Na+ must be supplied using a Na‐metal negative electrode to attain a high capacity in a half‐cell configuration. In this study, solid Na2CO3 powder was introduced into the P2−Na2/3Fe1/2Mn1/2O2 composite positive electrode as a sacrificial salt to compensate for the Na deficiency. Na+ was supplied through the electrochemical oxidative decomposition of Na2CO3 during the initial charging process; the decomposition mechanism responsible for this process was investigated in detail. Online electrochemical mass spectrometry confirmed that Na2CO3 was oxidatively decomposed in combination with the decomposition of the ethylene carbonate electrolyte. This reaction produced CO2, wherein the carbon source was derived from both Na2CO3 and the electrolyte. Consequently, Na+ supplementation improved the reversible capacity of the Na‐ion full cell. This study offers practical insights and a mechanistic understanding of the pre‐doping technique for Na‐free negative electrodes. This approach also compensates for the irreversible reductive capacity in a process that can be easily applied to practical sodium‐ and lithium‐ion batteries and capacitors.

Double-phase electrolyte enabling the long-lasting redox mediation in Li–O2 batteries

The achievement of practical Li–O2 batteries is impeded by their low discharge capacity, large charge overpotential, and short lifespan. In general, the use of electrolyte with a high-donor-number solvent such as dimethyl sulfoxide (DMSO) is able to drive the solution-mediated pathway, alleviating the premature passivation of cathode from the surface-mediated Li2O2 film growth, gaining large Li2O2 toroidal particles, and extending the discharge lifetime. However, direct electrochemical decomposition of Li2O2 toroidal products typically occurs at a high charge potential owing to the poor solid-solid contact between cathode catalysts and Li2O2 toroids. Besides, DMSO-based electrolytes are unstable to Li anode, leading to undesired parasitic reactions. To overcome above issues, herein, a double-phase electrolyte composed of 10-methylphenothiazine (MPT)-dissolved DMSO-based catholyte and octyltrimethoxysilane (TOOS)-based anolyte is designed taking advantages of the immiscibility of DMSO and TOOS solvents and the insolubility of MPT in TOOS. Benefiting from the rapid liquid-solid reaction between MPT+ and Li2O2 products, the blocked MPT shuttling in TOOS, and the good compatibility of TOOS-based electrolyte to Li anode, the assembled Li–O2 battery delivers a reduced charge overpotential and a robust cyclability over 250 cycles. This study provides a promising strategy for electrolyte design towards next-generation high-performance Li–O2 batteries.

Directing Fluorinated Solid Electrolyte Interphase by Solubilizing Crystal Lithium Fluoride in Aprotic Electrolyte for Lithium Metal Batteries

AbstractLithium fluoride (LiF) facilitates robust and fast‐ion‐transport solid electrolyte interphase (SEI) in lithium metal batteries. Fluorinated solvents/salts are ubiquitously employed to introduce LiF into SEI through electrochemical decomposition, but this approach is usually at the expense of their continuous consumption. A direct approach to fluorinate SEI that employs crystal LiF is limited by its poor solubility in the current battery electrolyte formulation. Dissolving crystal LiF in high‐dielectric‐constant solvents, like ethylene carbonate (EC) is nearly neglected. Herein, the feasibility of directly fluorinating SEI by the addition of crystal LiF in aprotic electrolyte with the assistance of EC is verified, and its mechanisms in fluorination of SEI and anti‐acidification of electrolyte are explored. The dissolved LiF is encapsulated by solvent‐/salt‐derived organic skins to promote the fluorinated SEI. Meanwhile, the presence of LiF in electrolyte alters hazardous thermodynamic equilibrium, suppressing the production of acid species to mitigate electrolyte acidification and SEI degradation. Such collective benefits yield a capacity retention ratio of ≈88% after 150 cycles at a high areal capacity (4.5 mAh cm−2) in Li||NCM622 cells. This facile and effective fluorination of SEI contributes to an in‐depth understanding of SEI formation and rational design of well‐performing lithium metal batteries.

100 W-class green hydrogen production from ammonia at a dual-layer electrode containing a Pt-Ir catalyst for an alkaline electrolytic process

Ammonia allows storage and transport of hydrogen over long distances and is an attractive potential hydrogen carrier. Electrochemical decomposition has recently been used for the conversion of ammonia to hydrogen and is regarded as a future technology for production of CO2-free pure hydrogen. Herein, a heterostructural Pt-Ir dual-layer electrode is developed and shown to achieve successful long-term operation in an ammonia electrolyzer with an anion exchange membrane (AEM). This electrolyzer consisted of eight membrane electrode assemblies (MEAs) with a total geometric area of 200 cm2 on the anode side, which resulted in a hydrogen production rate of 25 L h−1. We observed the degradation in MEA performance attributed to changes in the anode catalyst layer during hydrogen production via ammonia electrolysis. Furthermore, we demonstrated the relationship between the ammonia oxidation reaction (AOR) and the oxygen evolution reaction (OER).

Interfacial Electrochemical Lithiation and Dissolution Mechanisms at a Sulfurized Polyacrylonitrile Cathode Surface.

Advances in sulfurized-polyacrylonitrile (SPAN)-based cathode materials promise safer and more efficient lithium-sulfur (Li-S) battery performance. To elucidate electrolyte-cathode interfacial electrochemistry and polysulfide (PS) dissolution, we emulate discharge SPAN reactions via ab initio molecular dynamics (AIMD) simulations. Plausible structures and their lithiation profiles are cross-validated via Raman/IR spectroscopy and density functional theory (DFT). Lithium bis(fluorosulfonyl)imide (LiFSI) plays versatile roles in the Li-SPAN cell electrochemistry, primarily as the major source in forming the cathode-electrolyte interphase (CEI), further verified via X-ray photoelectron spectroscopy and AIMD. Besides being a charge carrier and CEI composer, LiFSI mediates the PS generation processes in SPAN electrochemical lithiation. Analysis of AIMD trajectories during progressive lithiation reveals that, compared to carbonates, ether solvents enable stronger solvation and chemical stabilization for both salt and SPAN structures. Differentiated CEI formation and electrochemical lithiation decomposition pathways and products are profoundly associated with the intrinsic nature of lithium bonding with oxygen and sulfur.

Charge compensation in a layered van der Waals NiPS3 host through various cationic intercalations

Electrochemical cation intercalation into 2D NiPS3 leads either to reduction of the (P2S6)4− units (Li example) or Ni cations (Na example), or causes electrochemical reduction and decomposition of EMIM cations within the van der Waals interlayers.

Deciphering the True FEC Reduction Mechanism and Its Implications to the Understanding of the SEI in Li-Ion Batteries

The main challenges in rechargeable batteries, especially when aiming for high energy density, arise from the limited electrochemical stability window of current state-of-the-art electrolytes. Negative electrode active materials, such as silicon, tin oxide and others, whose capacity is many times higher than that of graphite, often exhibit large volume expansion upon lithiation and therefore the SEI formed on their surface is unstable. The most popular strategy for improving their cycling stability is the use of electrolyte additives that are reduced at potentials more positive than the electrolyte solvents. Their decomposition products are incorporated in the SEI, leading to a more stable electrode/electrolyte interface.One of the most-investigated electrolyte additives is fluoroethylene carbonate (FEC), because it has been shown to lead to a significant performance enhancement of Si- and Sn-based anodes. Many reaction pathways have been proposed, however there is currently no agreement on the exact type of chemical compounds constituting the decomposition products, nor on the exact mechanism for FEC decomposition. To address these questions, we conducted a systematic study that tracked the morphological and chemical changes during electrochemical decomposition of FEC. We have found that despite FEC often being referred as a “film-forming” additive, the first stage of its decomposition leads instead to the formation of spherical particles, consisting mainly of lithium fluoride (see figure below);1 only later a carbonate-rich film covers the entire electrode, covering as well the LiF-rich spheres. This phenomenon has been overlooked before likely due to very simple reason, disclosed in our contribution.A detailed investigation using XPEEM—a surface-sensitive analytical technique with high lateral resolution—as a function of electrolyte composition shows that fluorine in the later-formed carbonate film comes from the electrolyte salt, while all fluorine from FEC decomposition resides in the spherical particles, formed upon FEC reduction. In addition, we have found that the size and amount of particles strongly depend on the cell medium, where electrolytes with higher dielectric constant lead to larger particle size, as does the presence of the high-capacity electroactive materials in the electrode, both contributing to the final properties of FEC-derived SEI. The results of this study provide a deeper understanding of how fluorine-containing additives work and enables tuning of the SEI properties to the desired morphological and chemical outcome by using the laws of simple crystal-growth theory by adjusting the inter-cell environment.This work demonstrates that, with the right analytical tools, the true nature of the even seemingly very-well studied compounds can be revealed and a full understanding of their decomposition mechanisms can be clarified. Acknowledgement This research was supported by InnoSuisse (Project number 18254.2) References Y. Surace, D. Leanza, M. Mirolo, Ł. Kondracki, C.A.F. Vaz, M. El Kazzi, P. Novák, S. Trabesinger, Energy Storage Materials 2022, 44, 156-167. Figure 1

Production of Cooking Gas through Electrochemical Decomposition of Organic Matter

In recent decades, the use of electrochemistry has increased exponentially. Electrochemistry has demonstrated their effectiveness in the cleaning of manufactured effluents and the decomposition of complex hydrological compounds for water treatment. Looking at the efficiency of the technology in the decomposition of organic matter, one wonders if it is not capable of doing more than just the de-pollution and treatment of water. Of course, there are other uses of electrochemistry, but in the literature, it is understood that it is used more for water treatment and de-pollution. This work is a review of the literature to identify the major works in electrochemical decomposition of organic matter to see to what extent this technology can be used for methane production (cooking gas) using pasty organic matter. The list of works appearing in this review is not exhaustive, but it is sufficient to give a clear idea of the technology, its progress and, above all, the challenges it faces. This review opens the way to other applications of electrochemical decomposition to meet today's energy challenges.

Introduction of Cationic Vacancies into NiFe LDH by In Situ Etching To Improve Overall Water Splitting Performance.

Nickel-iron layered double hydroxide (NiFe LDH) is still one of the hot catalysts for electrochemical water decomposition applications, despite its drawbacks, such as intrinsic activity and poor stability. In this work, the NiFe LDH-D1 electrocatalyst with cationic vacancies is successfully prepared by alkaline etching of Zn ion-doped NiFe LDH. The tightly arranged flocculated nanosheet structure on its surface provided a large active area. The cationic vacancies formed by strong alkaline etching not only promote the conversion of active phases such as NiOOH but also strengthen the stability of the electrode and the binding ability with oxygen so that the material has excellent catalytic properties along with alkaline long-term stability. At a current density of 10 and 100 mA cm-2, NiFe LDH-D1 shows a small voltage of 1.56 and 1.94 V, and at a current density of 200 mA cm-2, it performs well in a 72 h electrochemical water decomposition stability test. The present work demonstrates a simple etching strategy for cation vacancy engineering and provides an example of the construction of efficient bifunctional electrocatalysts with long-term stability.

Enhanced electrochemical activity of boron-doped nanocarbon functionalized reticulated vitreous carbon structures for water treatment applications

An extraordinary charge transfer kinetics and chemical stability make a boron-doped diamond (BDD) a promising material for electrochemical applications including wastewater treatment. Yet, with flat geometrical surfaces its scaling options are limited. In this study, the reticulated Vitreous Carbon (RVC) served as a substrate for boron-doped diamondized nanocarbons (BDNC) film growth resulting with complex heterogeneity carbon structures with different morphologies defined by using electron microscopy, microtomography, activation energy studies, and Raman spectroscopy.The proposed modification significantly boosted the electrochemical Fe(CN)63−/4− redox activity. The voltammetry and impedimetric studies revealed its origin as a significantly higher share of electrochemically active sites at the BDNC@RVC electrode (increased by 114 %) combined with enhanced heterogeneous rate constant (2× increase up to 8.24·10−4 cm s−1). Finally, to establish its applicability for water treatment, the BDNC@RVC was studied as the anode in electrochemical paracetamol decomposition. Boron-enriched nanoarchitecture formed at the RVC electrode surface substantially reduced the oxidation energy barrier manifested as a decrease in activation overpotential by 212 mV, which gave a consequence in a 78 % removal rate (in 4 h, at 0.7 mA cm−2), 12 % higher than bare RVC and yielding lower amounts of APAP decomposition intermediates.

An electrochemically transformed multifunctional binder network simultaneously strengthens the interphase stability and mechanical integrity of silicon anodes

Silicon (Si) is a promising alternative anode material for lithium-ion batteries due to its ultra-high theoretical capacity and suitable voltage platform. However, its practical application is limited by the rapid capacity fading caused by the instability of the solid electrolyte interphase (SEI) film, the collapse of Si particle structure and the mechanical failure of Si electrodes. Herein, we develop a multifunctional composite binder (denoted as PS) composed of multi-hydroxyl polyvinyl alcohol (PVA) and electroactive squaric acid (SA). The complete binder network derived from the efficient crosslinking reactions between SA and PVA chains, as well as the beneficial electrochemical synergistic decomposition reactions between SA and fluoroethylene carbonate additive, can effectively stabilize the macro- and micro-structures of Si electrodes, induce the beneficial decomposition components of electrolytes to build a robust SEI film, and promote the Li+ transport rate. Based on these beneficial effects, the optimized PS61-based Si anode exhibits higher initial coulombic efficiency (89.8 %), much improved rate performance (2041.5 mAh g−1 at 10 C), and better cycling stability (1582.1 mAh g−1 after 400 cycles) than that of the PVA-based Si anode. Furthermore, the NCM523//Si (PS61) full cell achieved a high reversible capacity of 140.8 mAh g−1 after 300 cycles, demonstrating the positive function of PS binder on promoting the practical application of Si anodes.

Carrageenan as A Sacrificial Binder for 5V LiNi0.5 Mn1.5 O4 Cathodes in Lithium-Ion Batteries.

5V-class LiNi0.5 Mn1.5 O4 (LNMO) with its spinel symmetry is a promising cathode material for lithium-ion batteries. However, the high-voltage operation of LNMO renders it vulnerable to interfacial degradation involving electrolyte decomposition, which hinders long-term and high-rate cycling. Herein, we overcome this longstanding challenge presented by LNMO by incorporating a sacrificial binder, namely, λ-carrageenan (CRN), a sulfated polysaccharide. This binder not only uniformly covers the LNMO surface via hydrogen bonding and ion-dipole interaction but also offers an ionically conductive cathode-electrolyte interphase layer containing LiSOx F, a product of the electrochemical decomposition of the sulfate group. Taking advantage of these two auspicious properties, the CRN-based electrode exhibited cycling and rate performance far superior to that of its counterparts based on the conventional poly(vinylidene difluoride) and sodium alginate binders. This study introduces a new concept, namely "sacrificial" binder, for battery electrodes known to deliver superior electrochemical performance but be adversely affected by interfacial instability. This article is protected by copyright. All rights reserved.

Decoupling the anodic and cathodic behavior in asymmetric electrochemical hydroiodic acid decomposition cell for hydrogen production in the iodine-sulfur thermochemical cycle.

The HI section of the iodine-sulfur (I-S) thermochemical cycle for hydrogen production is one of the most energy-intensive sections and with significant material handling challenges, primarily due to the azeotrope formation and the corrosive nature of the hydroiodic acid-iodine-water mixture (HIx). As an alternative, the single-step direct electrochemical decomposition of the hydroiodic acid (HI) to generate hydrogen can circumvent the challenges associated with the conventional multistep HI section in the I-S cycle. In this work, we present new insights into the electrochemical HI decomposition process by deconvoluting the contributions from the anodic and the cathodic sections in the electrochemical cell system, specifically, the redox reactions involved and the overpotential contribution of the individual sections (anolyte and catholyte) in the overall performance. The studies on the redox reactions indicate that the HIx solution output from the Bunsen reaction section should be used as the anolyte. In contrast, aqueous HI without any iodine (I2) should be used as the catholyte. In the anodic section, the oxidation proceeds with I2 as the final oxidized species at low bias potentials. Higher positive potentials result in iodate formation along with oxygen evolution. For the catholyte section, I2 and tri-iodide ion reduction precede the hydrogen evolution reaction when I2 is present along with HI. Furthermore, the potential required for hydrogen production becomes more negative with an increasing I2/HI ratio in the catholyte. Polarization studies were conducted with simultaneous deconvolution of the anodic and cathodic behavior in a two-compartment cell. Model fitting of the polarization data revealed that the anolyte section's activation overpotential is negligibly low. In contrast, the activation overpotential requirement of the catholyte section is higher and dictates the onset of hydrogen production in the cell. Furthermore, the catholyte section dominates the total overpotential losses in the cell system. Operation in the ohmic resistance-dominated zone resulted in close to 90% current efficiency for the electrochemical HI decomposition. The results highlight that the potential for process improvement lies in reducing the ohmic resistance of the anolyte section and in lowering the activation overpotential of hydrogen evolution in the catholyte section.

Fabrication of nanofibrous PbO2 electrode embedded with Pt for decomposition of organic chelating agents

A new fabrication method of nanofibrous metal oxide electrode comprising Pt nanofiber (Pt–NF) covered with PbO2 on a Ti substrate was proposed. Pt–NF was obtained by performing sputtering deposition of Pt on the surface of electrospun poly(vinyl alcohol) (PVA) nanofiber on a Ti substrate, in which PVA was then removed by calcination (Ti/Pt–NF). Subsequently, by introducing PbO2 to the Ti/Pt–NF using the electrodeposition method, a nanofibrous Ti/Pt–NF/PbO2 electrode was finally obtained. Because the Ti substrate was covered by nanofibrous Pt, it had no environmental exposure and thus, was not oxidized during calcination. The crystal structure of the PbO2 mainly consisted of β-form rather than α-form; the β-form was suitable for electrochemical decomposition and remained stable even after 20 h of use. The nanofibrous Ti/Pt–NF/PbO2 electrodes showed 10% lower anode potential, 1.6 times higher current density at water decomposition potential, lower electrical resistance in the ion charge transfer resistance, and 2.27 times higher electrochemically active surface area than those of a planar-type Ti/Pt/PbO2 electrode, and demonstrated excellent electrochemical performance. As a result, compared with the planar electrode, the Ti/Pt–NF/PbO2 electrode showed more effective electrochemical decomposition toward nitrilotriacetic acid (80%) and ethylenediaminetetraacetic acid (83%), which are commonly used as chelating agents in nuclear decontamination.

Fabrication of Hydroxyl‐Group‐Rich Reduced Graphene Oxide Film and its Application for Electrochemical Detection of Hydrogen Peroxide

AbstractGraphene oxide (GO) can be obtained economically from graphite, and it has, therefore, been used for energy storage, conversion, and biosensor fabrication. To overcome the limitations associated with the poor electrical conductivity of GO, mild thermal reduction is widely used. However, owing to considerable variations in GO in terms of size and shape, uniform reduction of GO films is highly challenging. Herein, it reports a mildly reduced uniform graphene oxide thin film (mrUG) that is enriched with functional hydroxyl groups. This film is effective for electrochemical H2O2 decomposition and detection. A uniform graphene oxide thin film (UGTF) is first fabricated on an indium tin oxide (ITO) substrate and subjected to mild thermal annealing at 300 °C. Remarkably, the variations in all important parameters, including film thickness, surface roughness, reduction level, are significantly low in the case of mrUG. Moreover, It is found that unlike GO, UGTF undergoes structural rearrangement easily and possesses many hydroxyl groups (─OH) when reduced for a specific duration (t = 10 s, mrUG(10)). mrUG(10) is highly stable and effectively decomposed H2O2, which is advantageous for the electrochemical detection of H2O2 with extremely low signal variations. Therefore, mrUG(10) can be used as a carbon‐based metal‐free electrocatalyst in biosensors, energy, and electronic applications.