Increase In Current Density Research Articles

Chemical growth of Niobium-doped vanadium pentoxide on aminated graphene for all-solid-state asymmetric supercapacitors

In this investigation, niobium-doped vanadium pentoxide (Nb–V2O5) was grown on the surface of amine-functionalized graphene nanosheets (NH2-Gr) using an in-situ hydrothermal method and explored the hybrid material as a positive electrode for the fabrication of an all-solid-state asymmetric supercapacitor (ASC). We have used KOH-loaded poly(acrylonitrile-co-1-vinylimidazole) (KOH/P(AN-Co-VIM)) gel as a solid electrolyte-cum-separator and exfoliated graphene (XGnP) as a negative electrode in the ASC. The morphological analysis of the Nb–V2O5/NH2-Gr hybrid revealed homogeneous growth of Nb–V2O5 on NH2-Gr nanosheets, while surface analysis confirmed a large fraction of mesopores with large surface areas in the hybrid. The hybrid electrode achieved a high specific capacitance of 1141.1 F/g at 1 A/g with 80.3% capacitance retention even after a 10-fold increase in current density, a significantly higher performance than a pure Nb–V2O5 electrode. As-assembled solid-state ASC device delivered a high energy density of 79.39 Wh kg−1 at a power density of 280.3 W kg−1, even though it retained high energy density at a higher power density of 12 kW kg−1. The ASC exhibited slow a self-discharge rate owing to the suppression of Ohmic leakage by the use of KOH/P(AN-co-VIM) gel electrolyte. Thus, the as-synthesized Nb–V2O5/NH2-Gr hybrid is an ideal alternative candidate for future supercapacitors.

Hydrogen production with a novel coaxial cylindrical electrolyser: A CFD study

This study introduces a unique coaxial cylindrical electrode design for Alkaline Water Electrolysers (AWEs) that is analyzed to show possible enhancements over the traditional stacked plate design. It investigates the performance of the proposed coaxial AWE for enhanced hydrogen production. Through comprehensive computational simulations, key performance indicators, such as current density and hydrogen volume fraction, are analyzed across various operating parameters. The results of this study indicate that the production rate of hydrogen achieves its highest level at a volume percentage of 3.4 %. This rate is significantly influenced by the concentration of the electrolyte, the distance between the cathode and anode rings, and, to a lesser degree, the porosity of the separator. Consequently, the optimized conditions demonstrate a promising increase in current densities, reaching 1000 mA/cm2 at an operating voltage of 2 V, showcasing the potential for developing more efficient and cost-effective AWE systems. This study further contributes valuable insights into the design and operational improvements needed for the advancement of large-scale hydrogen production technologies.

Electrodeposition of Silicon in the Low-Temperature LiCl-KCl-CsCl-K2SiF6 Melt Under Direct and Pulse Current

In this work, the effect of electrolysis modes and their parameters on the morphology of the silicon deposits on glassy carbon were studied. In direct current mode it was found that an increase in current density and deposition time changes the morphology of the silicon from a coating to a deposit with a complex surface. Scanning electron microscopy showed that silicon films produced at low current densities and a short deposition time are represented by spherical particles with a diameter of less than 1 μm. The pulse current mode made it possible to increase the cathode density of the deposition current, and the pulse current density to an average of ≈250 mA cm−2 does not lead to the formation of a large amount of dendritic deposit. It was found that a low frequency makes it possible to obtain higher-quality silicon coatings, because when the frequency increases, the coating most often does not cover the entire electrode. The high value of the duty cycle, even at low pulse current densities, always leads to the formation of dendrites. An increase in the total deposition time also leads to an increase in the amount of deposit and the formation of dendrites.

In-situ synthesis of synergistic ZnMn2O4/MnOOH nanocomposite as a cutting-edge pseudocapacitive electrode material for all-solid-state asymmetric supercapacitors

Currently, there has been a growing interest in constructing metal oxide composite structures through the in-situ synthesis method, especially for fabricating electrode materials for supercapacitors. This approach offers several advantages, such as improved contact between different materials, enhanced conductivity, efficient ion diffusion, and better overall electrochemical performance. This work investigates the synthesis of zinc manganese oxide and manganese oxyhydroxide (ZnMn2O4/MnOOH) composite using a solvothermal method. The structure, surface morphology, and composition of the ZnMn2O4/MnOOH composite were elucidated using standard physicochemical characterization techniques where the presence of ZnMn2O4 and MnOOH phases was confirmed and the ZnMn2O4/MnOOH nanocomposite behaved as a pseudocapacitive electrode with a notable specific capacitance of 1039.2 F g⁻1 at a current density of 1 A g⁻1. When subjected to a 10-fold increase in current density, the ZnMn2O4/MnOOH electrode maintained 50 % of its initial capacity, registering 513.4 F g⁻1. Additionally, the electrode showcased excellent cyclic stability, preserving 95 % of its initial capacity after 5000 cycles at 10 A g⁻1. Moreover, the constructed ZnMn2O4/MnOOH//activated carbon (AC) asymmetric supercapacitor (ASC) device attained a high energy density of 29.45 Wh kg⁻1 at a power density of 1384.5 W kg⁻1. The results confirm that the ZnMn2O4/MnOOH composite, prepared in a single synthesis step, shows great potential as a phenomenal pseudocapacitive electrode for energy storage applications.

Enhancement of mass transfer through under-rib convection in polymer electrolyte fuel cell with dimensionless moduli analysis

The significance of under-rib convection in the flow field development of polymer electrolyte fuel cells (PEFCs) is increasingly recognized. This study quantitatively evaluates the interplay between mass transfer and reaction processes in adjacent channels, affected by under-rib convection. A comprehensive analysis identifies that oxygen mole fraction and current density profiles in the channel-rib direction are governed by five dimensionless moduli. The effectiveness factor, defined as the ratio of the integral average under-rib current density to that without mass transfer resistance, elucidates the potential for current density enhancement due to under-rib convection. Experimental results demonstrate a significant increase in the under-rib current density from 0.15 to 0.32 A cm⁻2 as the pressure difference between adjacent channels rises from 0 to 929 Pa at 0.60 V and 0.52 relative humidity. This corresponds to an increase in the effectiveness factor from 0.37 to 0.77 and a Péclet number increase from 0 to 34.8. Model predictions indicate that the maximum net power density is achieved at a Péclet number of 60, balancing under-rib convection benefits and pumping pressure. Validated by experimental results, the model aids in reaction kinetics analysis and polarization prediction, offering significant insights and practical guidelines for electrochemical reactor optimization.

High-Efficiency Hydrogen Recovery from Corn Straw Hydrolysate Using Functional Bacteria and Negative Pressure with Microbial Electrolysis Cells

This study attempts to overcome the challenges associated with the degradation of complex organic substances like corn straw hydrolysate in hydrogen recovery by strategically enriching functional microbial communities in single-chamber cubic microbial electrolysis cells (MECs). We applied negative pressure, using acetate or xylose as electron donors, to mitigate the hydrogen sink issues caused by methanogens. This innovative method significantly enhanced MEC performance. MECs enriched with xylose demonstrated superior performance, achieving a hydrogen production rate 3.5 times higher than that achieved by those enriched with acetate. Under negative pressure, hydrogen production in N-XyHy10 reached 0.912 ± 0.08 LH2/L MEC/D, which was 6.7 times higher than in the passive-pressure MECs (XyHy10). This advancement also resulted in substantial increases in current density (73%), energy efficiency (800%), and overall energy efficiency (540%) compared with MECs operated under passive pressure with 10% hydrolysate feed. The enrichment of polysaccharide-degrading bacteria such as Citrobacter and Pseudomonas under negative pressure underscores the potential for their industrial application in harnessing complex organic substrates for bioenergy production in single-chamber MECs. This is a promising approach to scaling up bioenergy recovery processes. The findings of this research study contribute significantly to the field by demonstrating the efficacy of negative pressure in enhancing microbial activity and energy recovery, thereby offering a promising strategy for improving bioenergy production efficiency in industries.

Iron-vanadium redox flow batteries electrolytes: performance enhancement of aqueous deep eutectic solvent electrolytes via water-tuning

Deep eutectic solvents (DES) are being recognized as a highly promising electrolyte option for redox flow batteries. This study examines the impact of modifying the molar ratio of water to a DES consisting of urea and choline chloride on important measures of electrolyte performance, such as viscosity, cyclic voltammetry, and impedance spectroscopy. According to the findings, when the molar ratio of water to DES is 1:3, the viscosity of the electrolyte falls by 75 %, the peak current density increases by 5–9.5 times, the ionic conductivity increases by 5–10 times, and the ohmic resistance decreases by 60–90 %. This approach greatly enhances the conductivity and diffusion coefficient of the electrolyte, resulting in a novel, cost-effective, and highly efficient electrolyte for iron-vanadium redox flow battery applications. This study enhances the efficiency of DESs at the molecular level, establishing the foundation for future extensive implementations.

Raman Spectroscopy and Microstructural Characterization of Hot-Rolled Copper/Graphene Composite Materials

Given the increase in current density in the constituent materials of electrical systems, improving the electrical conductivity of these materials, particularly copper (Cu), is crucial. This would also help to mitigate the heat generated by Joule heating. The incorporation of graphene (Gr) into a composite material (Cu/Gr) is a viable solution. However, to ensure the proper transfer of properties between the reinforcement and the matrix, several elements must be considered, including the orientation of the reinforcement. As a 2D material, controlling graphene’s orientation within the structure is essential but often overlooked. To address this issue, hot rolling was implemented to improve the alignment of the reinforcement. The inclusion of graphene led to a 12 HV increase in the material’s hardness, demonstrating a positive composite effect. Simultaneously, rolling increased the material’s hardness from 67.6 to 75.1 HV by introducing more dislocations into the material. To characterize the graphene’s alignment, polarized Raman spectroscopy was used. This technique highlighted the improved alignment of the reinforcement in the rolling direction, a change that was visible and confirmed by scanning electron microscopy micrographs.

Exploring the adsorption of 4,4’-[oxalylbis(imino)]bis(2-hydroxybenzoic acid) layer at steel/biogasoline interface by the combined electrical-optical-simulation approach

Reactions at the steel/biogasoline interface trigger the adsorption of 4,4’-[Oxalylbis(imino)]bis(2-hydroxybenzoic Acid) (ODA) layer on the steel surface, thereby activating a mechanism that inhibited the early reactions. Exploring the conditionally deposited ODA layer requires a combined approach, including electrical, optical, and simulation techniques to track the film development and coating characteristics over time, and with the assistance of atomic force microscopy, quantum chemistry (DFT), and molecular dynamics (MD) simulations to reveal the adsorption mechanism of the ODA layer at steel/biogasoline interface. The four experimental ODA concentrations were conducted, related to the simulated un-coverage, undersaturated-, saturated-, and oversaturated-coverage model of the adsorbate on the adsorbent. The EC-RS data examines surface compositions and their distribution, coating/solution interface, and coating/substrate adhesion by, respectively, Raman spectroscopy (RS), electrochemical impedance spectroscopy (EIS), and current density—potential (I-V) scan. Namely, RS pointed out that an organic layer was established when ODA was added to the simulated biogasoline. EIS results revealed insulator behaviors of the ODA layer at the solid–liquid interface, limiting the charge transfer between the steel substrate and the biogasoline. I-V results showed an increase in surface current density and a decrease in surface polarization resistance of the coating with the rise in ODA concentration. The AFM morphology profile verified the degradation of the sample’s surface when exposed to biogasoline and the minimization of surface damage by ODA addition through adsorption. The simulation findings revealed that the adsorption of ODA on steel preferred physisorption, reaching the most stable state at a specified temperature and ODA concentration. The adsorption mechanism follows the Generalized Langmuir isotherm. The adsorbate (ODA molecules) can produce a transition phase with the steel substrate surface, which modifies the surface thermodynamic characteristics. The combined electro-optical-simulation technique can be applied to investigate various surface phenomena (reactions, catalyzes, adsorption). It especially helps to understand the protective mechanism of inhibitors in different media.

Boiling heat transfer characteristics of Cu–Al2O3 nanocomposite coating surfaces in distributed jet array impingement

Nanocomposite coating surfaces were electrodeposited on copper substrate at various current densities, deposition times and Al2O3 concentration to experimentally investigate the enhancement of boiling heat transfer of HFE-7100 under atmospheric pressure in a distributed jet array impingement. The surface structure topography and wettability were analyzed to explore their relation to boiling heat transfer enhancement and critical heat flux (CHF). An increase in both current density and deposition time led to a decrease followed by an increase in the wettability of the Cu– Al2O3 surface. Conversely, an increase in Al2O3 concentration resulted in decreased surface wettability. However, unlike pool boiling, jet impingement attenuated the impact of enhanced surface wettability on boiling heat transfer and CHF; instead, the microstructure on the surface was found to be closely linked to boiling heat transfer performance. The nanocomposite coating surfaces exhibited a 70 % higher maximum boiling heat transfer coefficient and 50 % higher CHF than those of smooth surfaces. Excessive Al2O3 concentration weakened the enhancement of heat transfer performance due to the inhibitory effect of Al2O3 nanoparticles on copper growth, leading to reduced micro-nano structures.

Fabrication of PSCs with light absorption chips utilizing double-metal-cladding waveguide technology

Metal nanoparticles or periodic metal nanostructures exhibit localized surface plasmon resonance (LSPR) effects, widely employed in photovoltaic devices to enhance the light absorption. In this study, we used a double-metal-cladding waveguide (DMCW) structure to fabricate hexagonal metal nanostructures on the front side of the indium tin oxide (ITO) glass, positioned away from the incident light direction. We then prepared perovskite solar cells under various reaction conditions. The analysis results indicate that the metal nanostructure chip excites near-field coupling, generating strong localized fields, and enhances the light absorption through the LSPR effect. The perovskite solar cells (PSCs) with the chip structures exhibited a significant increase in short-circuit current density (JSC) and fill factor (FF), accompanied by a decrease in dark current, indicating improved photovoltaic characteristics of the cells. Altering the evaporative deposition time of the silver film and the concentration of the reaction solution led to a 12.79% increase in the power conversion efficiency (PCE) of the PSCs.

Impact of Local Environment on Selectivity of Ag and Cu Gas Diffusion Electrodes with Strong Hydrophobic Substrate during the Electrochemical Reduction of CO2

Electrochemical CO2 reduction (CO2RR) is a promising pathway to convert detrimental CO2 emissions into sustainable fuels and chemicals, and close the carbon loop1. To ensure the industrial applicability of this technology, electrocatalysts need to be highly active, selective towards a desired product, and offer long-term stability. High activity can be achieved with gas diffusion electrodes (GDEs), in which the CO2 reactant is supplied directly from the gas phase, however reaching high selectivity toward a single product over time remains a challenge. Recently, the control of the local environment around the catalyst has been identified to be a key factor to ensure high selectivity and stability2.In this work, we show that the local environment around the catalyst drives the selectivity of the catalyst depending on the pore size and hydrophobicity of the GDE. GDEs with large pores and weak hydrophobicity lead to poor selectivity toward carbon products, while GDEs with small pore and strong hydrophobicity yield a greatly improved Faradaic efficiency (FE) towards CO in the case of Ag (FE > 70%)2 and towards C2H4 in the case of Cu (FE > 50%) 3 at 200 mA/cm2 for several hours. The further increase of current density is detrimental to the performance of the GDEs, which points to a limitation of the transport of CO2 to the electrocatalyst. Additionally, CO reduction experiments show a qualitatively similar behavior but at much lower current densities. These findings are consistent with the presence of an electrolyte layer wetting the electrocatalyst that forces the electrocatalytic reaction to take place at double phase boundaries. Finally, we provide evidence for the correlation between the loss of selectivity towards carbon products over time and the precipitation of carbonates by operando synchrotron X-rays diffraction experiments4.In summary, our results highlight the importance of controlling the local environment near the catalyst to enhance the selectivity towards carbon products during CO2RR. References 1A. Senocrate, C. Battaglia, J. Energy Storage 2021, 36, 102373 2A. Senocrate, F. Bernasconi, D. Rentsch, K. Kraft, M. Trottmann, A. Wichser, D. Bleiner, C. Battaglia, ACS Appl. Energy Mater. 2022, 5, 14504 3F. Bernasconi, A. Senocrate, P. Kraus, C. Battaglia, Energy & Environ. Science Catalysis, 2023, 1, 1009 4F. Bernasconi, A. Senocrate, N. Plainpan, M. Mirolo, Q. Wang, C. Battaglia, submitted

Separation of Lithium over Magnesium, Sodium, and Calcium By Electrodialysis Using Commercial Membranes

Lithium is considered a critical raw material worldwide due to the growing market for electric vehicles. Due to the risk of supply interruption in the short and medium term, alternative sources of lithium are being explored for battery supply. Among these, salt-lake brines have become a key supply because their abundance represents about 59% of lithium resources 1. A secondary source in the medium term is the recycling of spent Li-ion batteries by hydrometallurgical processes 2,3. Together, recovering lithium from brine and recycling can supply the demand for transport electrification. Conventional lithium extraction techniques from both brine and battery recycling face the challenge of selective separation over contaminants and low extraction efficiencies 4,5.As an alternative, electrodialysis (ED) is an important selective separation technique with high selectivity, productivity, and less consumption of chemical reagents under energy consumption. This electrochemical membrane separation process uses an electric field inducing anion and cation transport across alternating anion and cation exchange membranes. While standard electrodialysis can be used to desalinate water and generate more concentrated brine), selective electrodialysis processes that up-concentrate a specific ion from a mixed salt solution are less developed. Our goal with this work is to evaluate the effect of common ions on lithium separation by ED using three different commercial membranes. The experiments were carried out in a 4-chamber reactor where the feed solutions consisted of equimolar chloride salts of lithium and either nickel (representing battery recycling), magnesium, sodium, or calcium (representing brine). Anolyte, receiving, and catholyte chambers (Figure 1) contained 1.0 M H2SO4.Here, we present the results in terms of cation permselectivity, productivity, and energy consumption using three different commercial membranes for the cation exchange membrane in the ED setup: a standard cation exchange membrane (CXM-200), a monovalent cation exchange membrane (CXP-S) and a nanofiltration membrane (NF-90). The performance of each membrane was tested under varying applied current densities to assess the impact of operating conditions on ion transport. Results have demonstrated monovalent cationic membranes are strongly selective for lithium over magnesium and nickel, achieving selectivity of 43 and 57, respectively. The increase in current density from 2.8mA/cm² to 11.5mA/cm² also increased the fluxes of lithium and co-ions by the monovalent membrane, consequently decreasing the selectivity from 56.7 to 2.4. In addition, nickel precipitates in the feed chamber as the current density increases from 2.8mA/cm² to 5.7mA/cm². We then translate these results into a process model for upscaling the ED reactor, considering the species transport rate through the reactor chambers and selectivity for lithium. Keywords: battery recycling; brine; electrochemical membrane separation; critical raw materials.Figure 1: ED reactor used for lithium selective separation by commercial membranes References (1) Fuentealba, D.; Flores-Fernández, C.; Troncoso, E.; Estay, H. Technological Tendencies for Lithium Production from Salt Lake Brines: Progress and Research Gaps to Move towards More Sustainable Processes. Resources Policy 2023, 83 (January). https://doi.org/10.1016/j.resourpol.2023.103572.(2) Guimarães, L. F.; Botelho Junior, A. B.; Espinosa, D. C. R. Sulfuric Acid Leaching of Metals from Waste Li-Ion Batteries without Using Reducing Agent. Miner Eng 2022, 183 (May), 107597. https://doi.org/10.1016/j.mineng.2022.107597.(3) Martins, L. S.; Rovani, S.; Botelho Junior, A. B.; Romano Espinosa, D. C. Sustainable Approach for Critical Metals Recovery through Hydrometallurgical Processing of Spent Batteries Using Organic Acids. Ind Eng Chem Res 2023. https://doi.org/10.1021/acs.iecr.3c03048.(4) Asadi Dalini, E.; Karimi, G.; Zandevakili, S. Treatment of Valuable Metals from Leaching Solution of Spent Lithium-Ion Batteries. Miner Eng 2021, 173 (September), 107226. https://doi.org/10.1016/j.mineng.2021.107226.(5) Xu, S.; Song, J.; Bi, Q.; Chen, Q.; Zhang, W. M.; Qian, Z.; Zhang, L.; Xu, S.; Tang, N.; He, T. Extraction of Lithium from Chinese Salt-Lake Brines by Membranes: Design and Practice. J Memb Sci 2021, 635 (May), 119441. https://doi.org/10.1016/j.memsci.2021.119441. Figure 1

Water Transport Management in a Bipolar Membrane for CO2 Electrolysis Application

Bipolar membranes (BPMs) offer significant potential for electrochemical technologies, especially in CO2 electrolysis. Their unique ability to create pH gradients provides optimum chemical microenvironments at the cathode and anode for efficient, cheap and sustainable CO2 electrolysis. However, state-of-the-art BPMs are limited in their performance due to phenomena such as membrane degradation and membrane dehydration leading to low ionic conductivity, and hence their complete potential for various electrochemical technologies is yet to be realized. Previous studies have identified water transport as one of the main factors limiting the performance of BPM. A multi-physics model of BPM can serve as a useful tool to gain a comprehensive understanding of different performance limiting factors and thereafter propose solutions to overcome these limitations. The goal of the present study is to provide model based design guidelines for a BPM that facilitates efficient water transport, making it a suitable candidate for integration into a zero-gap CO2 reduction electrolyzer operating at industrial-grade performance levels.We have built a 1-D continuum model of a BPM kept in an aqueous (bi)carbonate electrolyte solution, incorporating physical phenomena such as water-dependent transport of ions and neutral species, field-enhanced homogeneous reactions (water-dissociation and acid-base reactions) along with CO2 phase transfer reaction at the BPM-aqueous electrolyte interfaces. The continuum model employs Poisson-Nernst-Planck equations to resolve local chemical species concentration. The effect of the electric field on the equilibrium dissociation constants of various charge-generating homogenous reactions is incorporated. This becomes important especially at interfaces within the domain where a sharp increase in electric field is observed. Unlike previous modeling studies, we also incorporate mass-conservation equation for water transport to resolve local water concentration inside the BPM. Local water concentration influences the transport of species in the BPM through their water-dependent activity and diffusivity. The electric potential distribution is resolved by incorporating water-dependent local permittivity of the BPM.Our model investigates both the reverse and forward bias operational modes of the BPM. In alignment with the experimental observation, in the reverse bias regime, the model identifies a distinct initial phase where current density is limited, with the majority of the current carried by protons and hydroxide ions at low overpotentials. As the potential increases, there's a rapid increase in current density, indicating a breakdown regime caused by an electric field-enhanced water dissociation reaction at the BPM interface. At even higher potentials, the polarization curve enters a third phase where the current density saturates characterized by water transport limitation. This aspect of the BPM polarization curve is uniquely captured by our model. Conversely, in the forward bias mode, as expected we do not observe any limitations due to mass transport, since water is generated at the bipolar junction. Here, the model forecasts a saturation of CO2 in the electrolyte, leading to gas bubbles forming at the BPM interface. To address the issue of water transport limitation, we conduct various parametric studies focusing on different membrane characteristics, such as individual layer thicknesses and their ion exchange capacities. The outcomes of these analyses provide crucial guidelines for optimizing these parameters and enhancing water management in BPM-based systems.

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.

Magnetic Field Driven Dynamic Reorganization of Electrocatalytic Interface for Sustainable Enhancement in Oxygen Evolution

Hydrogen with high calorific content (150 MJ/kg) and environment-friendly combustion product (H2O) becomes the alternative fossil fuel. Catalytic electrolysis of water is one of the attractive routes for generating H2. Energy-efficient and cost-effective electrolytic production of H2 has predominantly focused on lowering the overpotential for water splitting process by developing newer non-Pt group-based catalysts.This work demonstrates a new direction towards sustainable oxygen evolution reaction (OER) by exploiting the fundamental interplay of electromagnetic forces. Introducing an external magnetic field (Hext = 100 mT) perpendicular to the heterogeneous electrocatalytic interface produces an unprecedented increase in rate of electrocatalytic OER in phosphate buffer with pH=7. Such electromagnetic catalysis is achieved with metal phosphides (NiCoP and NiCoFeP) with different morphology, leading 2.5 fold increase in the OER current density and concomitant lowering of overpotential by 10% (Hext = 100 mT). Thereby, 50% lowering of charge transfer resistance (Rct) is achieved. This is substantiated by the lowering of the Tafel slope (by 5%) in the presence of Hext. Thus, we report two important observations influenced by the magnetic field: (a) direct effect of magnetic field on the catalyst surface to reduce the charge-transfer resistance, (b) spin-dependant OER process to get influenced under magnetic field and (c) indirect effect of magnetic field to sustain the magneto-electrocatalytic enhancement even after removing the magnetic field. The time-scale of magnetic relaxation is million times higher than conventional spin-lattice relaxation events in para/ferromagnetic systems. Such long-term stability of magnetized states is predominantly proposed to be originating from the NiCoP and NiCoFeP interface. So, we attribute the long-lived states to be additionally contributed from the volumetric expansion and active site expansion of the catalyst upon magnetization. Catalyst interface is arising due to the dendritic structure of catalyst. Such synergism of magnetization, is expected to increase the applicability of magneto-electrocatalysis as a more sustainable electrocatalytic approach towards a hydrogen-driven economy. Figure 1

(Invited) Development of Multifunctional Nanoscale Reactors for Electrocatalytic Oxidation of Dimethyl Ether Fuel

There has been growing interest in utilizing small (simple) organic molecules, as alternative fuels to hydrogen, for electrochemical energy conversion in fuel cells. Dimethyl ether (DME) is one of the possible choices in this respect. But electrooxidation of DME is rather slow at ambient conditions. Obviously, there is a need to develop novel electrocatalytic materials.Bimetallic PtSn catalysts were found to be almost as active as PtRu for methanol oxidation, and PtSn was even more efficient toward the electrooxidation of ethanol where breaking of C-C bond is required. While PtRu forms a single-phase homogeneous (intermetallic) alloy in which Ru is largely metallic, tin does not maintain its metallic state in PtSn (heterogenous alloy) and is transformed readily to such oxygenated species as Sn oxides or hydroxides. During operation of PtSn, the Pt component retains its mostly metallic character and act independently as Pt0 catalyst. By analogy to Ru, the Sn “bifunctional agent” tends to activate the water dissociative adsorption and increases population of chemisorbed hydroxyl groups to diminish the Pt-poisoning effect through enhanced oxidation of CO-type intermediates. Nevertheless, the DME oxidation on both PtRu or PtSn is still kinetically less favorable, relative to the systems’ performance toward methanol. While Sn, and particularly Ru alloyed atoms activate readily the water dissociative adsorption on Pt and permit the oxidative stripping of the poisoning CO-type adsorbates, the feasibility of the enhancement of the of the DME adsorption and activation through alteration of the electronic structure of Pt catalytic sites has not been fully explained. By analogy to the ethanol oxidation, Pt sites in the heterogeneous PtSn alloy are active toward dissociation of the DME molecule but the Sn additive is less efficient than Ru (from intermetallic PtRu) in the oxidative removal of poisoning adsorbates. But PtRu is probably the most active during oxidation of methanol, and this small organic molecule is also the DME-oxidation-reaction intermediate. Nevertheless, in comparison to bare Pt, electrooxidation of DME starts at PtRu and PtSn at less positive potentials.We pursue a concept of utilization of multicomponent hybrid electrocatalytic systems or nanoreactors utilizing zirconia oxide matrices for supporting and activation of primarily PtSn nanoparticles supported onto Vulcan XC-72 carbon black carriers. Electrocatalytic activity of Vulcan-supported PtSn (PtSn/V) nanostructured alloys supported onto ZrO2 matrices has been significantly enhanced toward electrooxidation of DME in acid medium (0.5 mol dm-3 H2SO4) by decorating PtSn/V with bimetallic PtRu nanoparticles. The enhancement effect concerns both shifting the onset potential for the DME-oxidation toward less positive values and increase of the DME electrocatalytic current densities recorded under both cyclic voltammetric and chronoamperometric conditions. The activating capabilities of ruthenium nanostructures seem to originate from the existence (even below 0.45 V vs. RHE) of reactive ruthenium oxo/ hydroxo groups on their surfaces capable of inducing the oxidative removal of poisoning (CO-type) adsorbates from the neighboring platinum catalytic sites. In this respect, the Ru-oxo species seem to support activity of Sn forming with Pt the PtSn heterogenous alloy. The PtSn/V admixed with PtRu decorated ZrO2 exhibit very high activity toward the oxidation of methanol which is also an important DME-oxidation intermediate. On the whole, the hybrid materials composed of Vulcan-supported PtSn decorated with Ru or PtRu nanoparticles decorated zirconia oxide seem to act as multifunctional nanoreactors inducing not only stripping of poisoning adsorbates but also catalyzing oxidation of the DME-reaction intermediates (methanol). Acknowledgement Authors acknowledge financial support of the National Science Center (Poland) under Opus Project 2018/29/B/ST5/02627.

Surface Ammonium Ions Assisted Decoration of Monodisperse Cobalt Nanoparticles on Molybdenum Oxide Films as Efficient Electrocatalysts for Hydrogen Evolution Reaction.

The high expense associated with electrocatalysts poses a challenge to the advancement of a hydrogen-based energy economy. The utilization of nonprecious metal-based electrocatalysts that are easily prepared and cost-effective is imperative for the future sustainability of a hydrogen society. The semiconductive MoO3-x has been identified as a promising nonprecious electrocatalyst for the hydrogen evolution reaction (HER). Nevertheless, enhancing its relatively low electrocatalytic activity toward HER remains a top priority. This study illustrates the manipulation of surface ammonium ions (NH4+) to produce uniform and distinct cobalt nanoparticles (Co NPs) on active MoO3-x supports, resulting in a more effective heterostructured composite electrocatalyst for HER. The presence of NH4+ ions in the MoO3-x film was extensively examined using infrared spectroscopy, X-ray photoelectron spectroscopy, and UV-visible colorimetric techniques. Additionally, the firmly attached NH4+ ions were employed as binding sites to precipitate Co-containing complex ions. Due to the monolayer-like adsorption of NH4+ ions, only a small quantity of Co precipitate was formed, which was subsequently electrochemically transformed into Co atoms that diffused and created well-separated uniform metallic Co nanoparticles (with an average size of less than 10 nm) on the MoO3-x film. The resulting heterostructure displays a 4.5-fold increase in current density for HER compared to the MoO3-x electrocatalyst through electrochemical assessments. The enhanced catalytic activity was ascribed to the optimized adsorption/desorption of the species involved in water reduction at the heterointerfaces and improved charge transfer rates. These nanoheterostructures hold great promise for a variety of applications in heterogeneous electrocatalysis, while the novel approach could potentially direct the creation of more heterostructures.

Dispersion of hydrophobic conductive carbon black (CB) in polytetrafluoroethylene (PTFE) emulsion through liquid bridges and fabrication of PTFE/CB composite film for triboelectric nanogenerators

Polytetrafluoroethylene (PTFE) is a highly electronegative material that is widely used in Triboelectric nanogenerators (TENGs). However, due to the ultralow surface energy of PTFE, it is difficult to achieve a stable and even dispersion of hydrophobic carbon black in the PTFE emulsion. In this study, a novel method was used to achieve a stable and uniform dispersion of hydrophobic carbon black in the PTFE emulsion. An interfacial modifier was added to form liquid bridges between PTFE emulsion particles. The hydrophobic carbon black was then dispersed among these liquid bridges, resulting in its uniform distribution within the aqueous emulsion. The addition of 0.75 wt% CB resulted in a 4.6-fold increase in open-circuit voltage and a 3.5-fold increase in short-circuit current density compared to pure PTFE. Moreover, after 10000 cycles, the open-circuit voltage remained mostly unchanged, indicating that it has great potential for use in wearable devices.

Semiconductor heterojunctions coated with reduced graphite oxide as electron transfer materials for high-performance perovskite solar cells

Exploring and insight into the relationship between the microstructure, light absorption performance, and carrier transport of perovskite light absorption layer materials and carrier transport layer materials is crucial for obtaining efficient and stable perovskite solar cells. We adopted a simple strategy to prepare a composite material known as reduced graphene oxide wrapped mesoporous hierarchical TiO2–CdS semiconductor heterojunctions (TiO2–CdS-RGO) as the electron transport layer in formamidine lead iodide perovskite solar cells. Compared with single TiO2 and binary composite, this composite material exhibits enhanced photoluminescence quenching, reduced photo generated carrier recombination rate, and improved electron transfer capability. Photovoltaic devices based on TiO2–CdS-RGO composite material showed a 14.5 % increase in short-circuit current density (JSC) and a 36.3 % increase in photoelectric conversion efficiency (PCE) compared to those with only TiO2. The improved optoelectronic properties observed with the TiO2–CdS-RGO as electron transfer layers can be attributed to several factors. On the one hand, mesoporous TiO2 with a high specific surface area is beneficial for perovskite infiltration and enhances electron transfer rate. On the other hand, the well-matching energy level structure among the three components aids in electrons extraction and reduces the recombination rate of photo generated charge carriers; In addition, RGO nanosheets with high conductivity serve as an efficient electron transfer network, providing a rapid charge transfer pathways, which is crucial for enhancing the photoelectric conversion performance of perovskite solar cells.