Reaction Kinetics Research Articles

Ag/Nico LDH Heterogeneous Structure for Efficient Alkaline Oxygen Evolution

Hydrogen is regarded as an ideal energy carrier owing to the highest energy density, presenting the possibility of substituting for traditional fossil fuels. Nowadays, water splitting is significant in producing large-scale hydrogen. However, the sluggish reaction kinetics during anodic OER, caused by the four-electron transfer, has hindered this energy conversion strategy. Although IrO2 and RuO2 are currently the representative OER electrocatalysts, their high cost and unsatisfactory performance limit their commercial application.Numerous electrocatalysts, including oxides, hydroxides, high-entropy alloy, metal organic frameworks, and their hybrids, have been developed to address this issue. Among them, layered double hydroxides (LDH) have demonstrated outstanding performance due to their highly adjustable structure, powerful host-guest interaction, and single-atomic-like active sites. NiCo LDH has attracted significant attention because of its appropriate atomic and electronic structure, intrinsic active sites and defects, compared with single-type Ni-based or Co-based catalysts. However, to meet the requirements of industrial production, a simple and scalable method to synthesize electrocatalysts with favorable OER activity and stability is imperative.We propose a facile and scalable strategy to synthesize Ag-decorated NiCo LDH (Ag/NiCo LDH) by electrodeposition and subsequent spontaneous redox reaction. A spontaneous redox reaction driven by the difference in standard redox potential of reactants can be applied to prepare heterogeneous catalysts in consequence of the facile process, tight combination between substrate and decorated materials, and no supplementary energy input. Silver metal, with its appropriate standard redox potential, good conductivity, and low cost compared to Iridium and Ruthenium, serves as a suitable decorated material. This strategy provides several advantages, for example, Ⅰ) optimizing the electronic structure of Ni and Co by the charge transfer from Ni, Co to Ag; Ⅱ) exposing more active surface area because of the heterogeneous structure, Ⅲ) improving the charge transfer capacity owing to the excellent conductivity of Ag nanoparticles, Ⅳ) increasing the stability of NiCo LDH due to the tight combination of Ag and NiCo LDH, Ⅴ) lowering the catalysts' price compared with Iridium and Ruthenium.The synthesized Ag/NiCo LDH exhibits enhanced OER performance in 1M KOH electrolyte, achieving an overpotential of 440 mV at a current density of 1000 mA cm-2 geo, surpassing that of NiCo LDH (722 mV at 1000 mA cm-2 geo). Surprisingly, Ag/NiCo LDH demonstrates exceptional durability, lasting over 425 h at 1000 mA cm-2 geo, an improvement of nearly eight-fold compared to NiCo LDH (50 h). This study provides a promising approach for developing efficient and stable electrocatalysts for alkaline oxygen evolution.

Electrochemical Detection of Ornidazole By Means of an Electrode Modified with Copper-Iron Nanoparticles and Carbon Black

Antibiotics have become fundamental tools in our fight against disease but their accumulation in the aquatic environment due to discharges from manufacturing plants, hospitals and farms, and to misuse by the public has seen them emerge as water pollutants. Their presence constitutes a serious environmental and health risk due to their toxicity and due to the risk of antimicrobial resistance (AMR), which may render antibiotics ineffective when employed to fight infection. Assessing the impact of antibiotic pollution on water quality, drinking water, recreational/bathing water, and the impact on life is critical for our health and wellbeing.Ornidazole is a member of the nitroimidazole antibiotic family that is heavily employed in the treatment of both human and animal infections [1]. This widespread use has led to the accumulation of the antibiotic in aquatic environments, posing a serious health risk due to its toxicity and the risk of AMR [2]. For this reason, novel and environmentally friendly methods of rapidly and accurately detecting its presence in the environment are vital to mitigate its pollution and harmful effects.In this study two materials are combined to enhance the conductivity and ability of a glassy carbon electrode sensor to detect ornidazole. Carbon black, a material composed of 95% carbon with a structure similar to graphite [3] is functionalized using a novel green method with tannic acid. This is then combined with a layered double hydroxide (LDH) to act as a source of metal nanoparticles. LDH’s are a combination of transition metals with the general formula [M1-x 2+M3+ x(OH)2]x+(An-)x/n.mH2O where M is two different metals and A is the intercalated anion between the stacked layers of M2+/M3+ ions to produce a 2D layered nanosheet structure [4]. These LDHs are synthesized hydrothermally, which involves combining sources of the desired metals into a sealed autoclave and heating to produce a high vapour pressure environment.Functionalized carbon black was dispersed and drop-casted onto the surface of the electrode. After drying, it was decorated by means of drop-casting with a dispersion of the LDH containing the desired elements. The LDH is then easily reduced by means of cyclic voltammetry to embed the nanoparticles of the desired elements into the carbon black, producing a stable modified electrode. LDH’s containing a variety of elements were investigated for their ability to detect ornidazole. The optimum element combination was concluded to be copper-iron nanoparticles. The procedure for the synthesis and modification of the electrode can be seen in Figure 1.The carbon black-copper iron (CuFe) modified sensor shows excellent sensitivity compared to bare glassy carbon and is capable of detecting ornidazole concentrations from 0.2 μM to 600 μM, displaying excellent stability over multiple uses. Studies were performed to characterize the carbon black-CuFe material using SEM, XRD, XPS, FTIR, and EDX. Investigations were carried out into the behaviour of the sensor at varying pH values and to determine the reaction kinetics of detection. To study the selectivity of the sensor interferants were introduced to the antibiotic solution and experiments were performed in real water samples gathered from various locations.[1] Q. Wang, C. Wang, Q. Wang, & Z. Wang, Journal of Agricultural and Food Chemistry., 2019, 67(41), 11527-11535[2] W. El, N. Tajat, A. Idelahcen, M. Tamimi, S. Qourzal, A. Assabbane, & I. Bakas, Microchemical Journal, 2023, 195, 109397[3] J. M. Martín-Martínez, Adhesion Science and Engineering : Surfaces, Chemistry and Applications, 2002, Chapter 13, 573-675[4] A., Karmakar, K., Kannimuthu, S., Sam Sankar, K., Sangeetha, R., Madhu, & S., Kundu. Journal of Materials Chemistry A. 2020 Figure 1

Ex Situ Synthesis of Ti3C2@Fe-Ni-NC Heterostructure Towards an Efficient Bifunctional Electrocatalyst for High-Performance Zinc-Air Batteries

Zinc-air batteries (ZABs) with sustainable electrocatalysts have seen a lot of efforts to address oxygen reaction challenges to increase their lifespan and energy efficiency. Metal-organic frameworks (MOFs) and their derived materials are potential bifunctional electrocatalysts for addressing the oxygen reactions kinetics. However, under operational circumstances, MOFs and derived materials typically exhibit subpar electrochemical and conductivity. In this study, embedding MOF derived FeNi-N-C porous material in a few layer MXene nanosheets was effective strategy, enabling adequate conductivity, stability, and exposure number of active sites with better electrocatalytic activity towards oxygen reduction and oxidation reactions (ORR and OER). The resulting FeNi-NC@Ti3C2 hybrid exhibits notable bifunctional activities with a half-wave potential of 0.85 V and a low overpotential of 1.56 V, remarkable long-term cycle durability, as well as strong alcohol tolerance in an alkaline electrolyte. In addition, there is conductive MXene scaffold to achieve the highest ORR and OER activities with an ΔE value of 0.70 V. Furthermore, the FeNi-NC@Ti3C2 air-cathode-based assembled ZAB exhibits remarkable long-term cycling stability at 10 mA cm-2, a peak power density of 201 mW cm-2, and a high open circuit voltage (OCV) of 1.5 V. Ti3C2 MXene nanosheets provide a synergistic effect between two different materials in addition to protecting the surfaces of composite. This work provides a useful technique for enhancing ZAB's oxygen redox reactions, which could be used to aid in the development of efficient MOF@MXene based catalysts for electrochemical energy reactions.

Development of Bifunctional Electrocatalyst for Overall Water Electrolysis: Vanadium and Phosphorus Dual-Doping Strategy on Ni3S2 Nanoneedle

Along with the rapid consumption of fossil fuels and serious environmental pollution, the development of renewable and clean energy has been receiving a lot of attention recently. Among the various renewable energy sources, hydrogen (H2) is considered as most promising substance in future energy society owing to its high gravimetric energy density and environmental friendliness. Electrochemical water electrolysis system is powerful strategy for high-purity hydrogen production without emission of any pollutants. It consists of two electrocatalytic reactions: oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). However, the practical efficiency of water electrolysis is limited due to the intrinsically sluggish reaction kinetics of OER and HER. To date, the precious metal-based electrocatalysts such as RuO2 and Pt/C for OER and HER, respectively, were employed as state-of-the-art electrocatalyst to enhance the performance of water electrolysis. However, due to the high expense, mono-functionality, and unsatisfactory stability of the precious metal-based materials, research on bifunctional electrocatalysts with low cost and high activity has become an urgent topic. To date, numerous scientific endeavors have been dedicated to the advancement of highly efficient non-noble metal-based bifunctional electrocatalysts such as transition metal oxides, hydroxides, sulfides, carbides, nitrides, and phosphides. Among these, Ni3S2 has emerged as a particularly promising electrocatalyst for water splitting, garnering substantial attention owing to its high electric conductivity, rich redox property, abundance in the Earth's crust, and environmentally friendly characteristics. Nevertheless, the electrocatalytic activity of Ni3S2 lags behind that of noble metal counterparts. Therefore, elaborate modification of Ni3S2 catalyst should be conducted to further improve its intrinsic activity toward OER and HER. Among the various strategies, heteroatom doping into Ni3S2 structure could be adopted as powerful technique for enhancement of electrocatalytic performance. The homogeneously incorporated dopants not only generate lattice disorders but elaborately modulate the surface electronic property. Specifically, high-valent cation dopants such as vanadium and molybdenum can effectively mediate the change of chemical states of Ni active sites during the step-wise electrocatalytic procedure. Meanwhile, additionally introduced anion dopants, which have lower electronegativity compared with sulfur, can reduce the electron trapping phenomenon induced by excessive electron transfer from nickel to sulfur. Inspired by above features, we synthesized V and P co-doped Ni3S2 nanoneedles directly grown on nickel foam (V-Ni3S2-P/NF) through facile two-step preparation method. First, V doped Ni3S2 nanoneedles were homogeneously grown on NF (V-Ni3S2/NF) by hydrothermal process without use of nickel precursor. The vanadium ions promote the nucleation of Ni3S2 species and lead the preferential growth toward 1D direction during the hydrothermal reaction. After that, the V-Ni3S2/NF was annealed in the tube furnace with the NaH2PO2 as a phosphorus precursor under the Ar flow. Under the mild annealing condition, the PH3 gases generated from thermal decomposition of NaH2PO2 reacted with the V-Ni3S2 species. Consequently, the V-Ni3S2 was partially phosphidated into V-Ni3S2-P throughout anion exchange process. As a result, the V-Ni3S2-P/NF electrocatalyst exhibited excellent bifunctional activity toward both OER and HER compared with mono-doped and un-doped counterparts and precious metal-based electrocatalysts. Furthermore, the outstanding electrocatalytic performance of V-Ni3S2-P/NF was well-maintained over the 100 h of continuous operation under alkaline condition. This study will contribute to the development of efficient and cost-effective electrocatalysts for future energy conversion and storage technologies.

Boron Modified Nife-MOF-74 Catalyst for Application in Advanced Anion Exchange Membrane Water Electrolyzers

Despite the promising potential of non-platinum group metal electrocatalysts for anion exchange membrane (AEM) electrolysis, their practical application remains a challenge.1 Metal–organic frameworks (MOFs) and their derivatives have gained significant attention due to their high surface area, 3D periodic porous structure, large porosities, diverse composition, and well-defined metal centers as potential OER electrocatalysts in AEM electrolysis.2 However, there is a limited research report that MOFs could be used in the membrane electrode assembly (MEA) test due to the inherent limitations, such as poor stability in water, especially under basic/acidic conditions and low electrical conductivities.3,4 To address these challenges, we present a novel approach involving the introduction of boron atoms into an aromatic carbon framework. In this study, we have successfully fabricated micro-nano flower-like bimetallic NiFe-MOF-74 doped with boron. These innovative materials exhibit exceptional catalytic activity, boasting an impressively low overpotential of 318 mV for OER at a laboratory-grade current density ranging from 10 to 100 mA/cm2. Moreover, they demonstrate rapid reaction kinetics, as evidenced by a small Tafel slope of 89 mV dec-1 in 1.0 M KOH solution. In addition, our research highlights the outstanding performance of boron-modified NiFe-MOF-74 as a robust anode material for AEM water electrolysis. This significant development paves the way for a promising electrocatalyst in the realm of anion exchange membrane water electrolysis. Our findings hold great potential for advancing the field and overcoming the existing challenges associated with non-platinum group metal electrocatalysts in AEM electrolysis.Reference:(1) Song, W.; Peng, K.; Xu, W.; Liu, X.; Zhang, H.; Liang, X.; Ye, B.; Zhang, H.; Yang, Z.; Wu, L.; Ge, X.; Xu, T. Upscaled Production of an Ultramicroporous Anion-Exchange Membrane Enables Long-Term Operation in Electrochemical Energy Devices. Nat Commun 2023, 14 (1), 2732. https://doi.org/10.1038/s41467-023-38350-7.(2) He, F.; Zheng, Q.; Yang, X.; Wang, L.; Zhao, Z.; Xu, Y.; Hu, L.; Kuang, Y.; Yang, B.; Li, Z.; Lei, L.; Qiu, M.; Lu, J.; Hou, Y. Spin-State Modulation on Metal–Organic Frameworks for Electrocatalytic Oxygen Evolution. Advanced Materials 2023, 35 (41), 2304022. https://doi.org/10.1002/adma.202304022.(3) Meena, A.; Thangavel, P.; Jeong, D. S.; Singh, A. N.; Jana, A.; Im, H.; Nguyen, D. A.; Kim, K. S. Crystalline-Amorphous Interface of Mesoporous Ni2P @ FePOxHy for Oxygen Evolution at High Current Density in Alkaline-Anion-Exchange-Membrane Water-Electrolyzer. Applied Catalysis B: Environmental 2022, 306, 121127. https://doi.org/10.1016/j.apcatb.2022.121127.(4) Zhang, B.; Zheng, Y.; Ma, T.; Yang, C.; Peng, Y.; Zhou, Z.; Zhou, M.; Li, S.; Wang, Y.; Cheng, C. Designing MOF Nanoarchitectures for Electrochemical Water Splitting. Advanced Materials 2021, 33 (17), 2006042. https://doi.org/10.1002/adma.202006042.

Recent advances in continuous flow synthesis of metal-organic frameworks and their composites.

Metal-organic frameworks (MOFs) and their composites have garnered significant attention in recent years due to their exceptional properties and diverse applications across various fields. The conventional batch synthesis methods for MOFs and their composites often suffer from challenges such as long reaction times, poor reproducibility, and limited scalability. Continuous flow synthesis has emerged as a promising alternative for overcoming these limitations. In this short review, we discuss the recent advancements, challenges, and future perspectives of continuous flow synthesis in the context of MOFs and their composites. The review delves into a brief overview of the fundamental principles of flow synthesis, highlighting its advantages over batch methods. Key benefits, including precise control over reaction parameters, improved scalability and efficiency, rapid optimization capabilities, enhanced reaction kinetics and mass transfer, and increased safety and environmental sustainability, are addressed. Additionally, the versatility and flexibility of flow synthesis techniques are discussed. The article then explores various flow synthesis methods applicable to MOF and MOF composite production. The techniques covered include continuous flow solvothermal synthesis, mechanochemical synthesis, microwave and ultrasound-assisted flow synthesis, microfluidic droplet synthesis, and aerosol synthesis. Notably, the combination of flow chemistry and aerosol synthesis with real-time characterization is also addressed. Furthermore, the impact of flow synthesis on the properties and performance of MOFs is explored. Finally, the review discusses current challenges and future perspectives in the field of continuous flow MOF synthesis, paving the way for further development and broader application of this promising technique.

Effective Lithium Polysulfides Anchoring on Vanadium Disulfide Facets for Lithium-Sulfur Batteries – A Computational Study

The commercialization of Li-S batteries is hindered by the shuttle effects of lithium polysulfides (LiPS) and the sluggish reaction kinetics. Hence, effectively trapping and promoting the conversion rates of LiPSs is of prime importance1. However, the fundamental kinetics of the electrocatalytic charging and discharging of Li-S batteries and the underlying mechanism have not been sufficiently explored yet.2 Therefore, by taking the 2D transition metal sulfide, VS2 as a model, we conducted a systematic investigation using density functional theory to study the ability of dominant exposed crystal planes of VS2 to trap LiPSs from leaching into electrolyte solvents and to act as an electrocatalyst to increase the Sulfur Reduction Reaction (SRR) kinetics3. To reflect a realistic environment of a battery, the effect of electrolyte solvents on the electrocatalytic activity was further investigated. Our calculations show that VS2 has moderate binding energy toward LiPSs which inhibits LiPS from leaching into electrolytes while fulfilling the key prerequisite to act as an electrocatalyst simultaneously.4 At the discharge, the conversion of S8 to the long chain Li2S8 was facile with a lower energy barrier while the rest of the reactions were sluggish explaining the accumulation of LiPSs. Further, the VS2 (001) facet exhibits excellent electrocatalytic activity for the SRR and Li2S decomposition reaction at charging compared to other dominant crystal planes, which significantly lowers the energy barriers of LiPS conversion during the charging and discharging process, ensuring high-rate performance and longer cycle life4. References Manthiram, A., Fu, Y., Chung, S.-H., Zu, C., & Su, Y.-S. (2014). Rechargeable Lithium–Sulfur Batteries. Chemical Reviews, 114(23), 11751–11787.Abraham, A. M., Thiel, K., Shakouri, M., Xiao, Q., Paterson, A., Schwenzel, J., Ponnurangam, S., & Thangadurai, V. (2022). Ultrahigh Sulfur Loading Tolerant Cathode Architecture with Extended Cycle Life for High Energy Density Lithium–Sulfur Batteries. Advanced Energy Materials, 2201494.Abraham, A. M., Boteju, T., Ponnurangam, S., & Thangadurai, V. (2022). A global design principle for polysulfide electrocatalysis in lithium–sulfur batteries—A computational perspective. Battery Energy, 20220003.Boteju, T., Abraham, A. M., Ponnurangam, S., & Thangadurai, V. (2023). Theoretical Study on the Role of Solvents in Lithium Polysulfide Anchoring on Vanadium Disulfide Facets for Lithium–Sulfur Batteries. The Journal of Physical Chemistry C.

Hetero-Bimetallic Paddlewheel Complexes for Enhanced CO2 Reduction Selectivity: A First Principles Study

The reduction of carbon dioxide (CO2) into value-added feedstock materials, fine chemicals, and fuels represents a crucial approach for meeting contemporary chemical demands while reducing dependence on petrochemical sources. Optimizing catalysts for the CO2 reduction reaction can entail employing first principles methods to identify catalysts possessing desirable attributes, including the ability to form diverse products, selectively form few products, or exhibit favorable reaction kinetics. In this study, we investigate the CO2 reduction reaction on bimetallic Cu paddlewheel complexes, aiming to understand the impact metal substitution with Mn, Co, or Ni has on bimetallic paddlewheel metal-organic frameworks (MOFs). Substituting one of the Cu sites of the paddlewheel complex with Mn results in a more catalytically active Cu center, poised to produce substantial quantities of formic acid (HCOOH) and minor quantities of methane (CH4) with a suppressed production of C2 products such as ethanol (CH3CH2OH) or ethylene (C2H4). Moreover, the presence of Mn significantly reduces the limiting potential for CO2 reduction from 2.22 eV on the homo-bimetallic Cu paddlewheel complex to 1.19 eV, thereby necessitating a smaller applied potential. Conversely, within the Co-substituted paddlewheel complex, the Co site emerges as the primary catalytic center, selectively yielding CH4 as the sole reduced CO2 product, with a limiting potential of 1.22 eV. Notably, the Co site faces substantial competition from H2 production, attributed to a lower limiting potential of 0.81 eV for hydrogen reduction. Our examination of the Cu-Ni paddlewheel complex, featuring a Ni substituent site, reveals two catalytically active centers, each promoting distinct reductive processes. Both the Ni and Cu sites exhibit a propensity for HCOOH formation, with the Ni site favoring further reduction to CH4, while the Cu site directs the reaction towards methanol (CH3OH) production. The significance of this study lies in its potential to inform and streamline future experimental efforts, facilitating the synthesis and evaluation of novel catalysts with superior capabilities for CO2 reduction.

Oxygen-Deficient Thermal Treatment Boosts Performance of Co-Ni-Fe Oxide Electrocatalyst in Oxygen Evolution Reaction

The production of green hydrogen through water electrolysis using electricity generated from renewable sources is one of the most promising strategies toward achieving a carbon-neutral economy.[1-3] Water electrolysis is an effective and well-established water splitting process consisting of two half-cell reactions, the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) at cathode and anode, respectively. Although hydrogen as the value-added product is generated at the cathode, the anodic reaction plays an important role in determining the reaction kinetics of the entire water splitting process due to the multiple-electron transfer.[4] Therefore, developing low-cost and highly active OER electrocatalysts is one of the keys to further improve overall efficiency of water electrolysis. Among various water electrolysis technologies, alkaline water electrolysis (AWE) has been commercialized for many decades and standing for medium-scale hydrogen production and using non-noble metals as electrocatalysts.[5]Co-, Ni-, and Fe- oxides or (oxy)hydroxides are reported as auspicious OER electrocatalysts for AWE, as well as abundance on earth.[6] In addition, oxygen vacancies in metallic oxides are reported recently as an effective approach to enhance catalyst activity for OER.[7] Herein, we present trimetallic oxides (CoNiFe oxides) annealed in different atmospheres which are oxygen-rich (A; air), an oxygen-poor (M; 1 vol% air in argon), and oxygen-free (H; 5 vol% H2 in argon), respectively, The CoNiFe (2:2:1)/M with a molar ratio of Co : Ni : Fe = 2 : 2 : 1 treated under an oxygen-poor atmosphere (M) exhibits the best performance in 1 M KOH, with an overpotential of 291 mV at 10 mA cm-2 geo, a mass activity at 1.56 V versus the reversible hydrogen electrode (RHE) of ~345 A g-1 catalyst, and a small Tafel slope of 32.0 mV dec-1. Moreover, CoNiFe (2:2:1)/M shows excellent stability in the OER process for at least 50 hours at 100 mA cm-2 geo at lab scale and ~75 h at 400 mA cm-2 in an alkaline electrolyzer. This work presents a simple and effective method to design OER catalysts based on trimetallic oxides with oxygen deficiencies for alkaline water electrolysis.

Molecular Solvation Environment Controls the Active Site in Cation-Mediated Electrocatalytic CO2 Reduction to Methanol

Electrocatalytic synthesis of higher-value products from waste molecules is an emerging technique for sustainable chemical catalysis. Heterogeneous molecular electrocatalysts are an important group of materials where the catalytic activity and selectivity can be controlled using molecularly defined active sites. Despite extensive efforts to synthesize better molecular catalysts, the effects of molecular aggregation, which dominates the interaction of the catalyst with the electrode surface as well as with the electrochemical solvation environment, are not fully understood. Using cobalt phthalocyanine (CoPc) dispersed on carbon nanotubes (CNTs) as a model system, we find that controlling the direct interaction of the molecular catalyst with cations in the electrochemical double layer (EDL) results in significantly enhanced performance for CO2 reduction (CO2RR). Specifically, molecular dispersion of the CoPc onto CNTs yields a 4-fold increase in total current density and 8-fold increase in methanol (MeOH) selectivity compared to aggregated CoPc physically mixed with the same CNT support, enabling CO2 to MeOH conversion with 42.34% Faradaic efficiency (FE). Using surface-selective sum-frequency generation (SFG) vibrational spectroscopy, direct detection of reaction intermediates reveals that the potential-dependent adsorption of two distinct CO intermediates at two types of active sites, one less active and producing mostly CO, the other more active and able to produce methanol. DFT calculations show that the CO intermediate responsible for selective MeOH production results from the direct interaction with cations present in the EDL. This interaction, which is only possible when CoPc is molecularly dispersed on the electrode surface, is responsible for the cation-assisted conversion of CO to MeOH. Control experiments using either strongly hydrated Li+, or chelated K+ by 18-crown-6-ether, which suppress MeOH formation, further confirms the important role of this interaction. Similarly significant enhancement effects are also observed for nitrate reduction reaction (NO3RR) and oxygen reduction reaction (ORR), showing that dispersing molecular catalysts into monomers states is a general design parameter required to enhance activity and selectivity by cation-assisted reaction kinetics inside the EDL.

High-Rate and Durable Zinc-Based Flow Batteries for Large-Scale Energy Storage

Large-scale energy storage is a key enabling technology for the widespread adoption of renewable energy such as wind and solar power. Among various technologies, zinc-based flow batteries stand out as one of the most promising candidates due to the high energy density, low cost, and use of earth-abundant active materials. However, the low operating current density and short cycle life resulting from notorious zinc dendrite formation, large internal resistance, and sluggish reaction kinetics pose a great challenge for their practical applications. Although great efforts have been made to address these issues, previous works mainly focused on one specific aspect, making it challenging to boost the overall performance of zinc-based flow batteries. In this presentation, a systematic study on the effects of key components on the electrochemical performance of zinc-bromine flow batteries will be presented. Our results show that all key components (electrodes, electrolytes, membranes, and flow fields) can exert a significant influence on the electrochemical performance. More impressively, a high areal capacity of >200 mAh/cm2 and an operating current density of as high as 400 mA/cm2 can be achieved by optimizing the design and operating parameters. Underlying mechanisms and perspectives for further improvement will be discussed during the presentation.

Influence of Microstructure on Defect Chemistry - Transport - Chemical Strain Coupling of (Pr,Ce)O2-δ Nanoparticles

Solid oxide fuel/electrolysis cells (SOFC/SOECs) are promising and environmentally-friendly technologies for meeting ever-increasing electricity and energy storage demands. Nanostructuring of SOFC/SOEC electrodes can enable improvement of the reaction kinetics and reduction of the operating temperature, owing to factors including the enlarged surface area, short diffusion lengths, and unique surface & interface properties. While the kinetic benefit is apparent, the effect of nanostructuring on other device-relevant physico-chemical properties cannot be neglected. Especially, the coefficients of chemical expansion (CCEs) are an important metric for mixed ionic-electronic conductors that can undergo changes in oxygen stoichiometry with variations in the surrounding atmosphere, temperature, and voltages during processing/operation. Chemical strains can cause cracking of monolithic parts during fabrication and delamination of electrodes from electrolytes in operation. CCEs are typically measured on bulk, polycrystalline materials with large particle or grain sizes. Therefore, it is important to understand the coupled transport and chemical expansion behavior in nano-ionic materials with large interface/surface density. This work aims to uncover the role of microstructure and nanoscale effects on the chemical strain and transport properties, through the lens of defect chemistry, with the goal of ultimately developing design principles for zero-strain materials with improved device lifetime and performance.Pr0.2Ce0.8O2- δ (PCO20) was selected as a model system and prepared as nanoparticles by a surfactant-free, low temperature co-precipitation method. (Pr,Ce)O2-δ compositions are valuable model oxide ion conductors to study, since both Pr and Ce can undergo changes of valence states under different temperature and pO2 regimes to accommodate oxygen stoichiometry excursions. Prepared nanoparticle samples were first in-situ sintered in the dilatometer at three different temperatures (600 ⁰C, 725 ⁰C, 850 ⁰C) to induce and evaluate microstructure evolution. The chemical strain and electronic/ionic conductivity were then studied on stable microstructures with different average particle sizes at lower temperatures by simultaneous in-situ dilatometry and electrochemical impedance measurement (EIS) upon changing pO2 at different isotherms (550 to 400 ⁰C). At each isotherm, all the samples expand as pO2 decreases. From the conductivity vs. pO2 measurements, the maxima at certain pO2 indicate the dominant polaron mechanism of the electronic transport, consistent with the measured conductivity activation energy. However, samples with lower sintering temperatures exhibit less pO2 dependence of the conductivity, which implies a transition in the mixed ionic/electronic conduction behavior toward higher ionic transference numbers as particle size decreases. Correspondingly, the chemical strains associated with losing oxygen monotonically decrease with the decrease of the sintering temperature, and hence the particle size. The chemical strain vs. oxygen stoichiometry dependence and corresponding CCEs were quantified as function of particle size and temperature by combining thermogravimetric analysis (TGA) with the dilatometry results and in-situ X-ray diffraction. The particle size, chemical composition, valence states, and morphology of samples after CCEs measurements were also compared using XRD, SEM, and S/TEM-EELS, with the latter indicating the expected differences between bulk and surface defect chemistry. Implications of the results for size-dependent defect chemistry and its influence on chemical strains and redox CCEs will be further discussed. Keywords: redox, chemical expansion, defect chemistry, mixed ionic electronic conduction, ceria, chemo-mechanics, nanoparticle, thermogravimetric analysis, dilatometry, impedance

Single Atom Catalyst Anchored on Nitrogen-Doped Porous Carbon As an Effective Sulfur Host for Lithium-Sulfur Batteries

Lithium-sulfur batteries (LSBs) are considered highly promising for next-generation energy storage due to their high theoretical specific capacity and energy density. However, challenges such as the insulating nature of sulfur cathodes, the detrimental shuttle effect of lithium polysulfides (LiPSs), and sluggish conversion kinetics of LiPSs during charge/discharge cycles impede their commercial viability. In this study, we employed a facile ‘dissolution-carbonization’ approach to synthesize nitrogen-coordinated monometallic atomic catalysts anchored on mesoporous carbon to promote surface-mediated reactions of LiPSs. The hierarchical porous carbon support physically confines the sulfur species, while the introduction of single atoms efficiently captures polysulfide intermediates and facilitates their redox conversion kinetics with a lower activation energy barrier. The synergistic effect of the single atom and nitrogen-rich porous carbon (NC) significantly enhances reaction kinetics and sulfur species utilization. Consequently, LSBs incorporating single-atom catalysts (SACs) demonstrate remarkable performance metrics, including high-capacity retention (824.2 mAh g−1), superior Coulombic efficiency (>98.5%), low-capacity decay rate (0.042% per cycle) after 500 cycles at 1 C, and excellent rate capability (776 mA h g–1 at 3 C). This work presents an effective strategy that combines the functions of a nanoporous material host and SACs for lithium-sulfur batteries.

High-Performance Lithium-Sulfur Batteries with Atomic V- and Co-Modified Ketjen Black-Sulfur Composite Cathode

Lithium-sulfur (Li-S) batteries are potential alternatives to lithium-ion batteries, which are known to have certain drawbacks. This has drawn special technological attention. Sulfur’s low electrical conductivity, shuttling of the intermediate polysulfides, the slow conversion reaction kinetics of various lithium polysulfides (LiPS), and the major volume change of sulfur in the lithiation reaction are some of the main issues that still need to be resolved before Li-S batteries can be used in practical applications. Additionally, it is likely because there are not enough prognostic models determining energy densities at the cell and pack level based on materials and cell design, most of the articles do not report system-level metrics, specific energy (Wh kg-1), and energy density (Wh L-1).To overcome these problems, atomic vanadium (V) and cobalt (Co) modified ketjen black-sulfur composite (VCKBS) was prepared and used as a cathode in Li-S batteries. The synthesized composite was characterized by various techniques, e.g., XRD, Raman, SEM, HR-TEM, HAADF-STEM, and XPS spectra. The polysulfide adsorption test showed that V had increased the adsorption ability, and cyclic voltammetry displayed the increased catalytic activity resulting from Co, offering a large number of interfacial active sites and ensuring smooth electron transfer. Cycling performance tests showed an initial specific capacity of 1329 mAh g−1, maintained at 1249 mAh g−1 after 100 cycles. Under a higher sulfur loading (2.4 mg cm−2), at 0.2 C, Li-S cells demonstrated an initial specific capacity of 1201 mAh g−1 and retained 985 mAh g−1 after 300 cycles with a low fading rate of 0.059% per cycle. The rate performance tests showed that the prior capacity is nearly recovered, going from 1C back to 0.1C, demonstrating the superiority of the VCKBS material.In addition to the experimental characterization of the Li-S cell performance, energy densities were also predicted by a proposed system-level performance model. The 1st and 100th discharge capacities were used to forecast the system-level specific energies and energy densities. The system-level specific energies and energy densities based on the 100th discharge capacity of VCKBS cathodes had improvements of 1342 and 568%, respectively. This suggests that an easy route to construct the highly stable cathode material may pave the way for the development of highly efficient Li-S batteries. Acknowledgments Hira Fazal acknowledges support from the Türkiye Scholarship/Research Fellowship Program sponsored by the Prime Ministry of Turkey Presidency for Turks Abroad and Related Communities (21PK070917). Damla Eroglu acknowledges support from the Istanbul Development Agency (Award No: TR10/21/YEP/0001). We also thank the National Natural Science Foundation of China (22171180) and the Science and Technology Commission of Shanghai Municipality (20520710400).

Simulation of Electrical Conductivity of Porous Composite Electrodes for Solid Oxide Cells Using a Monte Carlo 3D Equivalent Electronic Circuit Networks

Solid oxide cells (SOCs) show high potential in energy conversion applications necessary for the decarbonization of the economy. Their advantage consists in ability to operate at high temperatures, reaching up to 900 °C. Firstly, it results in accelerated electrode reactions kinetics, secondly, in favorable thermodynamic conditions decreasing the equilibrium voltage of the water splitting. As a result, SOCs are attractive candidates for both efficient electrolysis and fuel cell applications, offering a robust solution in the pursuit of clean energy. However, the elevated operational temperature also introduces material challenges that hinder the competitiveness of SOCs.Porous gas diffusion electrodes are used to accomplish the desired electrode reactions. Considering conventional exclusively electron-conductive electrode materials, triple phase boundary (TPB) is required for the reactions to take place – a simultaneous contact of electron-conductive, ion-conductive and gaseous phase. While the electrode and electrolyte phases are solid, the gaseous phase is represented by open porosity in the electrode body. TPB is located exclusively at the contact area of electrode and electrolyte components in the case of single-phase electrodes, limiting the electrode electrocatalytic performance. To avoid the limitation by TPB length, composite electrodes are frequently used. Due to the involvement of the ionically conductive phase, they exhibit improved electrocatalytic capabilities.Electrolyte phase, however, usually exhibits 4 orders of magnitude lower electrical conductivity than the electron-conductive phase, while gaseous phase is electrically non-conductive. Thus, an improper phase composition and morphology of the composites can lead to a significant drop in their electrical conductivity and thus in the cell performance. Simple and reliable method for the conductivity value prediction is up to now missing. At the same time, experimental determination is both expensive and time-consuming. The goal of this study was to develop simple, fast and reliable method for prediction of electrical conductivity of the porous electron-ion conductor composites.The key feature of the presented approach lies in the minimal requirements for input parameters. Only electrode phase composition and bulk electrical conductivity of each phase are required. Based on the input composition, the model generates a 3D artificial specimen, a domain discretized into cubic voxels each assigned randomly to a specific phase. The resulting structure is substituted with an equivalent circuit network with electric elements corresponding to the electrochemical properties of the material components: specific resistivity of electrical conductors and polarization resistance / capacitance of electrochemical reaction at material interface. In-silica electrochemical impedance spectroscopy measurement is performed by solving charge balance following Kirchhoff’s current law for multiple frequency values. Resulting impedance spectrum is fitted in order to obtain Ohmic and polarization resistance and the capacitance of the artificial specimen. This procedure is averaged over a large number of artificial specimens in a Monte Carlo manner.Conventionally used oxygen electrode composite material lanthanum strontium manganite (LSM) mixed with yttria-stabilized zirconia (YSZ) was used to produce validation dataset. LSM:YSZ powder mixtures of compositions between 1:0 and 0:1, chosen to produce samples of various degree of LSM percolation, were homogenized. The mixtures were fired at 1150 °C. Electrical conductivity of the pellets was determined at temperatures between 600 and 800 °C using electrochemical impedance spectroscopy.Experimental data obtained were confronted to the model results. The model demonstrated very good accuracy for a porosity value of up to 55%. Significant error was observed in the porosity range between 55% and 68%. Finally, the model failed to generate an artificial specimen with a porosity of 75%. As it was found, the limited applicability of the model for the materials characteristic for high porosity was caused by the coalescence of the void phase. This shortcoming of the model was solved by implementing morphological parameter describing degree of void phase coalescence in the electrode structure. Due to this modification, model allows to gain valuable information on the microstructure of the studied composite material on the base of the experimentally determined conductivity data.This work introduces a novel modelling approach with minimal amount of input parameters, streamlining the prediction of electrical conductivity of porous electron-ion conductor composites. This simplified yet effective methodology holds great promise for efficiently characterizing and optimizing materials for energy conversion applications, offering a valuable tool for advancing research in the field.This publication was supported by the project "The Energy Conversion and Storage", funded as project No. CZ.02.01.01/00/22_008/0004617 by Programme Johannes Amos Commenius, call Excellent Research.

Microstructure Evolution of Electrodeposited Magnesium on Copper Current Collector during Cycles for Anode-Free Rechargeable Magnesium Battery

Rechargeable magnesium (Mg) batteries attract lots of interest owing to their high theoretical volumetric energy density and low cost from the natural abundance of Mg. Additionally, Mg is less prone to dendrite growth during charging, which improves the battery safety. However, rechargeable Mg battery systems suffer from sluggish reaction kinetics on the electrodes and poor cycle life, greatly limiting their practical competitiveness. While most studies of rechargeable Mg batteries focus on the development of electrolytes and their feasibilities, the microstructure evolution of the Mg metal anodes during cycles is not fully unveiled. Furthermore, when using Mg metal as the anode, the excessive Mg may limit the overall energy density of the cells. Recently, anode-free battery systems were introduced to further improve the battery capacity. In this report, we investigated anode-free rechargeable magnesium batteries by electrodepositing Mg on a copper (Cu) current collector in an all phenyl complex (APC) electrolyte. Afterward, the microstructure evolution of the electrodeposited Mg after discharge/charge cycles was studied.The electrodeposited Mg on the Cu current collector with a current density of 2.25 mA/cm2 and a capacity of 1.5 mAh/cm2 shows a uniform distribution of Mg grains with an average grain size of 1.14 ± 0.06 μm. Subsequent Mg stripping with half the deposited capacity (0.75 mAh/cm2) was conducted at various current densities. Stripping with intermediate current density (0.75 mA/cm2) results in non-uniform discharge holes and possible local exposure of the Cu current collector, which could deteriorate the anode integrity. In contrast, the stripped electrodeposited Mg at relatively large (2.25 mA/cm2) and small (0.25 mA/cm2) discharge current densities show dense and uniform discharged holes on the surface. After prolonged discharge/charge cycles at a relatively large current density (2.25 mA/cm2), the electrodeposited Mg still exhibits a uniform surface morphology. In addition to cycling the electrodeposited Mg, a Mg-sulfur (Mg-S) full cell was also assembled with an anode of electrodeposited Mg on Cu and a sulfur/graphite cathode to explore the potential of anode-free rechargeable Mg-S battery. Figure 1

Effect of Experimental Parameters on the Electrochemical Current during Scanning Electrochemical Microscopy of Living Cells

Scanning Electrochemical Microscopy (SECM) is gaining popularity for its application to live cell imaging to monitor electrochemical processes occurring at the interface of living cells and electrodes. [1] Although many studies have been reported varying the instrumental parameters and using various probe designs, [2] the influence of experimental parameters on the electrochemical current must not be neglected, in order to generate reliable results. Our work explores parameters, such as temperature, light exposure and cell media during the SECM analysis of Adenocarcinoma Cervical cancer (HeLa) cells. The experimental and numerical studies with temperature variation revealed that temperature changes of 2ᵒC influence the reaction kinetics of single living cells. [3] Further, it was observed during light exposure that the electrochemical current becomes stabilized after 20 minutes of constant light environment compared to dark, where the standard deviation of the electrochemical current showed an increase in trend overtime. Furthermore, electrochemical current responses of HeLa cells in Phosphate Buffered Solution (PBS), Dubelcco’s Modified Eagle Medium (DMEM) and DMEM with 10% Fetal Bovine Serum (FBS) is being explored. These results will help to understand the origin of potential electrochemical current changes and the ideal experimental conditions to perform SECM measurements with living cells.[1] I. Beaulieu, S. Kuss, J. Mauzeroll, M. Geissler, Biological scanning electrochemical microscopy and its application to live cell studies, Anal. Chem. 83 (2011) 1485–1492. https://doi.org/10.1021/ac101906a.[2] D. Polcari, P. Dauphin-Ducharme, J. Mauzeroll, Scanning Electrochemical Microscopy: A Comprehensive Review of Experimental Parameters from 1989 to 2015, Chem. Rev. 116 (2016) 13234–13278. https://doi.org/10.1021/acs.chemrev.6b00067.[3] N. Thomas, D. Lima, D. Trinh, S. Kuss, Temperature Effect on the Electrochemical Current Response during Scanning Electrochemical Microscopy of Living Cells, Anal Chem. 95 (2023) 17962-17967. https://doi.org/10.1021/acs.analchem.3c03716

Nanoparticulated Vanadium Oxide on BiVO4 for Boosting Photoelectrochemical Glycerol Oxidation

Hydrogen (H2) has been spotlighted as ideal energy carrier due to its relatively higher energy density compared to fossil fuel and no carbon emissions during the energy generation. However, most of current produced H2 comes from as byproducts in fossil fuel reforming processes. To reduce dependence on fossil fuel in the H2 production process, photoelectrochemical (PEC) water splitting is considered as promising strategy for producing H2 using sustainable resources. Nevertheless, the insufficient efficiency in PEC water oxidation oxygen evolution reaction (OER) has limited overall PEC water splitting system efficiency due to its relatively high oxidation potential and sluggish catalytic kinetics. Furthermore, the low value of generated oxygen has been pointed out as obstacle from an economic perspective. To overcome these challenges, glycerol, byproduct of biodiesel, has been attracted numerous attentions as PEC oxidation resource since it has three hydroxyl groups and relatively lower oxidation potential than OER. Furthermore, glycerol oxygenated value-added products like dihydroxyacetone (DHA) can improve economics of PEC hydrogen production system. Upon these strengths, PEC glycerol oxidation reaction (GOR) provides improved strategy that generates value-added products in anodic part and green energy source (H2) in cathodic part simultaneously, which can replace PEC water splitting. Bismuth vanadate (BiVO4) is one of the most promising transition metal oxide based catalyst for PEC GOR due to its relatively narrow bandgap, high theoretical photocurrent density and deep positive valence band maximum (VBM) position. Additionally, although the surface kinetics of BiVO4 for OER has been sluggish, it potentially would be advantage for GOR with high production rate. However, the relatively instability of BiVO4 in acidic electrolyte during operation and lower selectivity of oxygenated products has hindered their practical application in PEC GOR. To solve these problems, introduction of nanoparticles as cocatalysts has been much studied for ameliorating surface kinetics and passivation the surface of photoanode. However, the interface between nanoparticles and photoanode with poor chemical interaction can induce the higher interfacial resistance and slow charge transfer efficiency rather. In this study, we present in-situ vanadium oxide (VOx) nanoparticle decoration on the surface of BiVO4 (VOx/BiVO4) via selective etching process using alkaline treatment for enhancing PEC GOR and we report the world best photocurrent density based on BiVO4 photoanode for GOR with high selective DHA production. VOx nanoparticles with an average size of 5 nm by selective etching process using alkaline treatment is decorated on the surface of BiVO4. The VOx promotes the surface reaction kinetics via modulating the fermi level and enhanced photovoltage of BiVO4 and improves long-term stability for GOR by compensation of V5+ and Bi3+, which combines both efficiency and stability. Furthermore, the surface decorated photoanode presents a 6.82 mA/cm2 (1.34-fold improvement) photocurrent density at 1.23 V versus the reversible hydrogen electrode (RHE) under 1 sun illumination, which has been attributed enhanced catalytic kinetics with upshifted fermi level and photovoltage of BiVO4. Moreover, the long-term stability of VOx/BiVO4 has been exhibited over 10 hours and the high selectivity for DHA is achieved. This study presents insight into the role vanadium of selective etched VOx on the surface of BiVO4 with low valence state than that of BiVO4 and improving the potential of BiVO4 based catalyst as GOR photoanode for high selective value-added DHA production using solar energy.

Cyclic Olefin Copolymer-Based Reinforced Anion Exchange Membrane for Fuel Cell

Alkaline exchange membrane (AEM)-based fuel cells have emerged as a promising technology for clean energy conversion. In contrast to acidic proton exchange membrane in fuel cells, AEM fuel cells utilize an alkaline membrane AEM to facilitate the migration of hydroxide ions, offering advantages of economic earth-abundant catalysts and enhanced electrochemical reaction kinetics. However, AEMs that possess all characters of high ion conductivity, good chemical stability under high pH and temperature, robust mechanical properties, scalable synthesis, and low manufacturing costs are rare until now.Herein, we present quaternary ammonium-functionalized cyclic olefin copolymers (COCs) as a new class of alkaline stable and low-cost AEMs. Furthermore, we developed reinforced composite AEM by impregnating the quaternary ammonium-functionalized COC into a mechanically robust matrix. The prepared COC-reinforced membrane exhibits outstanding hydroxide conductivity of 127 mS/cm at 80°C and low swelling ratio in liquid water, and excellent mechanical properties with a tensile strength > 50 MPa, and elongation at break > 248%. The H2-O2 fuel cell test exhibited a maximum peak power density of >1.2 W cm-2 at 80°C with a low high-frequency resistance (HFR) under 0.1 Ohm cm2.

Hollow-Structured Co-MoSx/Graphene Trifunctional Electrocatalyst for Self-Powered Hydrogen Production System.

Developing a single electrocatalyst that can facilitate both rechargeable aqueous metal-air batteries and water splitting has become a crucial focus in renewable-energy technologies. This necessitates addressing the three distinct electrocatalytic reactions: the electrochemical oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). Despite significant efforts, the creation of a alkaline medium based trifunctional catalyst with high activity at a low cost has proven to be a considerable challenge. Currently, Pt and its alloys have been considered as the most active catalysts for the ORR and HER, whereas noble-metal oxides such as IrO2 and RuO2 are considered as the golden standards of OER catalyst. However, noble-metals based catalyst have been suffered from their high cost, limited reserves in the Earth’s crust, and poor electrocatalytic stability. Moreover, these noble metals face challenges in simultaneously exhibiting trifunctional catalytic activity for ORR, OER, and HER. In recent study, Transiton metal sulfides(TMSs) have great attraction as trifunctional catalyts due to their eqrth abudance, tunnable band structure, and crystal structure. especially, one of widely used TMCs is MoS2 because of their Pt-like high catalytic activity for HER as well as thermodynamic electrochemical stability and rich catalytic sites in the planar nature. However, the most stable 2H (hexagonal) phase MoS2 suffers from poor electrical conductivity, low wettability, and aggregation indced reducing active catalytic sites and resulting high resistance. 2H MoS2 also shows poor activity for OER and ORR, thereby hampering its practical applications as trifunctional catalyst. To overcome this threshold, various strategies have been conducted to improve their electrochemical charateristics, such as defect engineering, heterojunction foramtion, phase transform and integrating porosity control. However, commonly considered method to synthesis requires complex multi-steps with high temperature, vaccum system, explosive gas, and toxic etchant.In this study, we successfully synthesized the homogeneous growth of a Co-based nanometer-scale metal-organic framework (MOF) on graphene oxide at room temperature. Furthermore, a facile one-pot solvothermal method was employed to synthesize Co-MoSx/Graphene, which consists of a hollow, heterogeneous bimetallic sulfide (Co3S4/MoS2 with Co-S-Mo bonding) within a sandwiched graphene/MoS2 layer, demonstrating superior trifunctional activity and stability. Incorporating a conductive graphene layer between MoS2 layers is an effective strategy for not only realizing high electrical conduction to MoS2 layers, but also increasing MoS2 interlayer spacing for high ion accessibility. Besides, a variety of techniques, including Cs-corrected scanning transmission electron microscope (Cs-STEM), X-ray diffraction(XRD), and X-ray absorption spectroscopy (XAS), are used to confirm the atomic configurations of Co-MoSx/Graphene structure and morphologies. Also, Raman, Fourier-transform infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS) were conducted to investigating the binding structure and chemical states. Furthermore, The internal electric field (IEF) within heterojunction, which induced from the differing electron density of the bimetallic species and the sandwiched graphene are contribute not only electron density structure optimization for enhancing reaction kinetics but also accelerating electron-hole exchange. The IEF in the microporous-heterostructure accelerates the diffusion of reaction intermediate with sufficient mass transport and facilitates a Graphene/MoS2-to-Co-MoSx pathway for enhancing redox kinetics of sluggish OER and ORR. Consequently, the OER and ORR-inactive MoS2, HER, and ORR-inactive Co3S4, along with less catalytically effective graphene, demonstrate outstanding performance when combined in the bimetallic sulfide based highly active heterojunctional structure. To investigate the electrochemical catalytic properties of Co-MoSx/Graphene, Rotating disk electrode(RDE) was used with three electrode measurment. The presence of MoS2/Graphene on Co3S4 and Co-MoSx bonding species in Co-MoSx/Graphene enhances the alkaline electrochemical catalytic activity by reducing overpotential and Tafel slopes(220 mV, 110 mV dec-1 in HER and 320 mV, 55.8 mV dec-1 in OER) under 1M KOH solution. Moreover, the ORR performance was evaluated by using Koutecky-Levich (K-L) Plot with different rotating speeds under 0.1M KOH. The electron transfer number (n) is closed theoretical value of 4.0 also shows outstanding performance of the onset potential, half-wave potential and kinetic current density (0.88 V, 0.67 V, and 10.4 mA cm-2), which is comparable that of Pt/C (0.92 V, 0.8 V, and 10.3 mA cm-2). Furthermore, Co-MoSx/G based rechargeable Zinc-Air battery achieve over 85% of theoretical zinc utilization efficiency and 1.4 times higher power density than a Pt/C + RuO2 air cathode based system. We believe that this work could provide a rational strategy for achieve trifunctional electrocatalyst and high performance self-powered hydrogen production system.This research was supported by the National Research Foundation of Korea (2022M3H4A1A04096482, RS-2023-00229679) funded by the Ministry of Science and ICT.