Electrocatalytic Activity Research Articles

Investigating the Electrocatalytic Oxygen Evolution Reaction of Hydrothermally Synthesized NiFe2O4 Nanoparticles

In this study, nickel ferrite (NiFe2O4) nanoparticles were synthesized using the hydrothermal method at various pH values. The objective was to investigate the influence of pH variation on particle size and electrocatalytic activity. The formation of cubic phase nanoparticles was confirmed through X-ray diffraction (XRD) analysis. To characterize the electrochemical properties, the nickel ferrite nanoparticles were coated onto a stainless steel substrate using the doctor blade technique. The microstructural analysis was conducted using scanning electron microscopy (SEM). The samples were further analyzed using linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS). The average crystallite size, determined from the XRD pattern, was approximately 40 nm. SEM images revealed a conversion from nanoplates to a granular morphology. The synthesized electrode exhibited an overpotential of 392 mV at 10 mA/cm2 and demonstrated good stability for 5 hours. These findings highlight the excellent electrocatalytic activity of nickel ferrite nanoparticles for the oxygen evolution reaction (OER).

Investigation of overall water splitting process on the 1 T/2H-MxCS catalyst via in situ Raman and IR spectroscopy measurement

The decomposition and formation of water molecules determine the protonation and deprotonation processes at the catalyst surface. Detecting interfacial water is particularly challenging because it is located between two condensed phases. Herein, we combine electrochemical in situ Raman and infrared spectroscopy with computational techniques to study the interfacial water on snowflake-like 1 T/2H-xMoS2/Cu2S (1 T/2H-MxCS). The snowflake-like Cu2S prevents the aggregation of modified MoS2 nanoflowers. The 1 T/2H-M0.02CS electrocatalyst exhibits excellence electrochemical performance, with a low overpotential of 59 mV and Tafel slope of 56 mV dec−1. This outstanding property can be ascribed to the interface and the formation of 1 T-MoS2, which not only decreases the activation energy required for the reduction reaction but also provides additional active sites for the catalytic reaction. Density functional theory calculations (DFT), in-situ Raman, and FT-IR spectroscopy were used to further elucidate the mechanism of electrocatalytic performance. This strategy offers new insights into enhancing the electrocatalytic activity of transition metal sulfides and a deep understanding of the HER mechanism.

Developing TiCo2O4 spinel based on rGO nanosheet to enhance electrochemical performance of OER activity

The reduction of fossil fuel reserves and the deterioration of environmental conditions have led to a worldwide concern with producing significant amounts of energy in a sustainable manner. The production of electrocatalysts for the oxygen evolution reaction (OER) is imperative for widespread commercialization of water electrolyzers. The electrocatalysts must exhibit improved electrocatalytic behavior while being cost-effective. This work presents simple hydrothermal route for producing a TiCo2O4 nanostructure with a spherical morphology, which is supported on reduced graphene oxide sheets (rGO). The nanocomposite has been subjected to an investigation of its morphological, structural and electrochemical characteristics. This material exhibits promise for electrochemical water splitting due to its significant electroactive surface area, distinctive morphology and metal ions (M+) synergetic effect on its electrocatalytic performance. The nanostructure of TiCo2O4/rGO-has been observed to exhibit robust electrocatalytic activity, underscoring the significance of the present study. Additionally, presented are the enduring stability of the OER, along with the reduced overpotential (269 mV@10 mA cm−2), decreased Tafel slope (37.56 mV dec-1) with greater electrochemical active surface area. Our finding suggests that the TiCo2O4/rGO nanohybrid exhibited high electrocatalytic efficiency and can be utilized in diverse electrochemical applications.

Ba-leaching-initiated structural destabilization of perovskite Ruthenates during the oxygen evolution reaction

The destabilization of a lattice structure during the oxygen evolution reaction (OER) is one of the most essential aspects for designing and realizing highly efficient electrocatalysts. However, the underlying mechanism of structural evolution or degradation at the microscopic scale on the electrocatalyst surface during the OER has not been elucidated because of the sluggish yet dynamic character of the reaction. To address this issue, the direct observation of the unstable electrocatalytic activity is necessary. In this study, we demonstrate that the structural destabilization of epitaxial cubic perovskite BaRuO3 thin films during the OER originates from Ba leaching, Ru dissolution, and oxygen vacancy. A thin film geometry is adopted to selectively visualize the structural decomposition at the well-defined sample surface. The cubic BaRuO3 thin film initially exhibits high OER activity, which drastically decreases even during the first cyclic voltammetry cycle and is completely lost after the first cycle. The OER activity loss is closely related to the generation of structural defects on the surface, indicating the absence of the Ba and Ru atoms. This study proposes the mechanism underlying the OER activity that can be extended to elucidate the structural destabilization in various Ru- and Ir-based oxide catalysts.

Amorphous MoS2 from a machine learning inter-atomic potential.

Amorphous molybdenum disulfide has shown potential as a hydrogen evolution catalyst, but the origin of its high activity is unclear, as is its atomic structure. Here, we have developed a classical inter-atomic potential using the charge equilibration neural network method, and we have employed it to generate atomic models of amorphous MoS2 by melting and quenching processes. The amorphous phase contains an abundance of molybdenum and sulfur atoms in low coordination. Besides the 6-coordinated molybdenum typical of the crystalline phases, a substantial fraction displays coordinations 4 and 5. The amorphous phase is also characterized by the appearance of direct S-S bonds. Density functional theory shows that the amorphous phase is metallic, with a considerable contribution of the 4-coordinated molybdenum to the density of states at the Fermi level. S-S bonds are related to the reduction of sulfur, with the excess electrons spread over several molybdenum atoms. Moreover, S-S bond formation is associated with a distinctive broadening of the 3s states, which could be exploited for experimental characterization of the amorphous phases. The large variety of local environments and the high density of electronic states at the Fermi level may play a positive role in increasing the electrocatalytic activity of this compound.

Synergistic Bulk and Surface Engineering for Expeditious and Durable Reversible Protonic Ceramic Electrochemical Cells Air Electrode.

Reversible protonic ceramic electrochemical cells (R-PCECs) offer the potential for high-efficiency power generation and green hydrogen production at intermediate temperatures. However, the commercial viability of R-PCECs is hampered by the sluggish kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) within conventional air electrodes operating at reduced temperatures. To address this challenge, we introduce a novel approach based on the simultaneous optimization of bulk-phase metal-oxygen bonds and in-situ formation of a metal oxide nano-catalyst surface modification. This strategy is designed to expedite the ORR/OER electrocatalytic activity of air electrodes exhibiting triple (O2-, H+, e-) conductivity. Specifically, our engineered air electrode nanocomposite-Ba(Co0.4Fe0.4Zr0.1Y0.1)0.95Ni0.05F0.1O2.9-δ demonstrates remarkable ORR/OER catalytic activity and exceptional durability in R-PCECs. This is evidenced by significantly improved peak power density from 626mW cm-2 to 996mW cm-2 and highly stable reversibility over a 100-hour cycling period. This research offers a rational design strategy to achieve high-performance R-PCEC air electrodes with superior operational activity and stability for efficient and sustainable energy conversion and storage. This article is protected by copyright. All rights reserved.

In Situ Construction of Biphasic Boride Electrocatalysts on Dealloyed Bulk Ni-Mo Alloy as Self-Supporting Electrode for Water Splitting at High Current Density.

Nickel-molybdenum-boron (Ni-Mo-B)-based catalysts with biphasic interfaces are highly advantageous in bifunctional electrocatalytic activity in alkaline water-splitting. However, it remains an ongoing challenge to obtain porous Ni-Mo alloy substrates that provide stable adhesion to catalysts, ensuring the long-term performance of bifunctional self-supporting electrodes at a high current density. Herein, a porous Ni-Mo alloy substrate was effectively obtained by a cost-effective dealloying process on a commercial Ni-Mo alloy with high-energy crystal planes. Subsequently, the Mo2NiB2/Ni3B bifunctional catalyst was in situ synthesized on this substrate via boriding heat treatment, resulting in outstanding catalytic activity and stability. Density functional theory (DFT) calculations reveal that the abundant biphasic interfaces and surface-reconstructed sites of the Mo2NiB2/Ni3B catalyst can decrease the energy barriers for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively. Thus, the designed self-supporting electrodes show bifunctional catalytic activity with overpotentials of 151 mV for HER and 260 mV for OER at a current density of 10 mA cm-2. Markedly, the assembled water electrolyzer can be driven up to 10 mA cm-2 at 1.64 V and maintain catalytic activity at a high current density of 1000 mA cm-2 for 100 h. The new strategy is expected to provide a low-cost scheme for designing self-supporting bifunctional electrodes with high activity and excellent stability and contribute to the development of hydrogen energy technology.

Novel electrochemical ZnO/MnO2/rGO nanocomposite-based catalyst for simultaneous determination of hydroquinone and pyrocatechol.

An innovative electrochemical sensing method is introduced for dihydroxy benzene (DHB) isomers, specifically hydroquinone (HQ) and pyrocatechol (PCC), employing a zinc-oxide/manganese-oxide/reduced-graphene-oxide (ZnO/MnO2/rGO) nanocomposite (NC) as an electrode modifier material. Comprehensive characterization confirmed well-dispersed ZnO/MnO2 nanoparticles on rGO sheets. Electrochemical analysis revealed the ZnO/MnO2/rGO-NC-based modified electrode possesses low electrical resistance (126.2 Ω), high electrocatalytic activity, and rapid electron transport, attributed to the synergies between ZnO, MnO2 and rGO. The modified electrode demonstrated exceptional electrochemical performance in terms of selectivity for the simultaneous detection of HQ and PCC. Differential pulse voltammetry studies validated the proposed sensor's ability to detect HQ and PCC within linear response ranges of 0.01-115 μM and 0.03-60.53 μM, with detection limits of 0.0055 µM and 0.0053 µM, respectively. Practical validation using diverse water samples showcased excellent percent recovery of HQ and PCC using the ZnO/MnO2/rGO-based electrochemical sensor, underscoring the sensor's potential for real-world applications in environmental monitoring.

Metal-organic frameworks derived low-cost Cu-doped Co3O4 for efficient reduction of ultra-low nitrate concentrations to ammonia

The electrochemical reduction of nitrate to ammonia represents a potential approach for the valorization of waste, offering the dual benefit of mitigating various environmental concerns and concurrently yielding the valuable product of ammonia. However, on the way to its further application, the lacking of low-cost and efficient electrocatalysts under low nitrate concentrations is still one pressing issue because of the intense hydrogen evolution reaction (HER) competition and many by-products. Herein, metal–organic frameworks (MOF) derived low-cost Cu-Co3O4/NF exhibits excellent electrocatalytic activity in the low nitrate concentrations (2 mmol/L), attaining the ammonia yield rate of 0.076 mmol h−1 cm−2 and 92.4 % Faradic efficiency at −0.53 V vs. RHE. The combined results of In-situ FTIR and theoretical calculation reveal the atomic hydrogen reduction pathway, decrease in free energy of intermediate reactions and inhibition of HER of Cu-Co3O4/NF. This work introduces one economical, efficient and simple strategy and further demonstrates the superior effect of MOF derivatives in fascinating low nitrate concentration reduction to ammonia.

Metal–Support Interaction in Pt Nanodisk–Carbon Nitride Catalyst: Insight from Theory and Experiment

Metal–support interaction plays a critical role in determining the eventual catalytic activity of metals loaded on supporting substrates. This interaction can sometimes cause a significant drop in the metallic property of the loaded metal and, hence, a drop in catalytic activity in the reactions, especially in those for which low charge carrier transfer resistance is a necessary parameter. Therefore, there should be a case-by-case experimental or theoretical (or both) in-depth investigation to understand the role of support on each metal. Here, onto a layered porous carbon nitride (g-CN), we grew single crystalline Pt nanodisks (Pt@g-CN) with a lateral average size of 21 nm, followed by various characterisations such as electron microscopy techniques, and the measurement of electrocatalytic activity in the O2 reduction reaction (ORR). We found that intercalating Pt nanodisks in the g-CN interlayers causes an increase in electrocatalytic activity. We investigated the bonding mechanism between carbon support and platinum using density functional theory and applied the d-band theory to understand the catalytic performance. Analysis of Pt’s density of states and electronic population across layers sheds light on the catalytic behaviour of Pt nanoparticles, particularly in relation to their thickness and proximity to the g-CN support interface. Our simulation reveals an optimum thickness of ~11 Å, under which the catalytic performance deteriorates.

Significant Enhancement of Electrocatalytic Activity of Nickel-Based Amorphous Zeolite Imidazolate Frameworks for Water Splitting at Elevating Temperatures

Significant Enhancement of Electrocatalytic Activity of Nickel-Based Amorphous Zeolite Imidazolate Frameworks for Water Splitting at Elevating Temperatures

A novel layered cobalt oxide Ba2Co9O14 as an efficient and durable bifunctional oxygen electrocatalyst for rechargeable zinc-air batteries

In this work, a layered cobalt oxide Ba2Co9O14 (BCO), belongs to a Ban+1ConO3n+3(Co8O8) family composed by alternating CdI2 based layers (Co8O8) with n (111) perovskite blocks (Ban+1ConO3n+3), has been developed as a potential bifunctional oxygen electrocatalyst candidate for efficient and durable rechargeable zinc-air battery (ZAB) application. Because of the greatly increased the specific surface area caused by ball-milling, the as-milled BCO material exhibits strongly enhanced bifunctional electrocatalytic activity towards oxygen reduction and oxygen evolution reaction in alkaline medium. Moreover, the assembled BCO-based ZAB yields an effectively improved maximum output power density of 166 mW cm−2, a considerable specific capacity of 789 mAh g−1, and excellent charge-discharge cycle stability of over 250 h at 10 mA cm−2 with over 1500 cycles.

A novel copper ion enhanced electrochemical DNA biosensor for the determination of epinephrine

A novel electrochemical biosensor was developed for the detection of epinephrine (EP) by immobilizing double-strand DNA (dsDNA) bound with copper ions on a gold electrode (Cu2+/dsDNA/MCH/AuE). The electrochemical behavior of EP at Cu2+/dsDNA/MCH/AuE was examined, and the results demonstrated a significant enhancement in the electrocatalytic oxidation peak current of EP due to the formation of a stable G-Cu(II)-G sandwich structure between Cu2+ and guanine at the modified electrode. The modification process of the electrode was characterized by scanning electron microscopy, infrared spectroscopy, electrochemical impedance spectroscopy, and differential pulse voltammetry. A study on the effect of pH in phosphate buffer solution on the electrochemical oxidation of EP indicated that the catalytic oxidation process was pH-dependent. A plot of catalytic current versus EP concentration exhibited a dual-linear relationship within two ranges: 1.0–12.5 μM and 12.5–1000.0 μM, with correlation coefficients of 0.995 and 0.997, respectively. The limit of detection was determined to be 47 nM (S/N = 3). According to the calculated Hill coefficient (0.99), it can be concluded that the electrocatalytic process followed the Michaelis-Menten kinetic mechanism. The maximum catalytic current Im was 25 μA, while the apparent Michaelis-Menten constant Km was 1.425 mM. These findings indicated excellent electrocatalytic activity of the modified electrode towards oxidation of EP. The developed biosensor successfully detected EP in spiked mouse serum as well as epinephrine hydrochloride injection with high selectivity, sensitivity, stability, and accuracy.

Tailoring Electrochemical Water Oxidation Activity from the Isostructural Series of Alkaline‐Stable Bimetallic Fe,Ni‐Azolate Metal–Organic Frameworks

AbstractIncorporating electrocatalytic active sites into the reticular framework allows for the design of novel catalytic structures promoting desired catalytic reactions with efficient mass transfer. However, to fully exploit the advantages of such a framework, it is crucial to ensure the electrochemical stability of the material. In this context, alkaline‐stable bimetallic MxNi2‐xCl2BTDD (M = Fe, Co) metal–organic frameworks (MOFs) are employed as electrocatalysts for alkaline water oxidation reaction (WOR) to understand the correlation between secondary metal incorporation and catalytic activity changes. For a specific Fe ratio within the MOF, the optimal catalytic activity is achieved at an overpotential of 315 mV at a WOR current density of 10 mA cm−2geo. Based on its well‐defined crystal structure and uniformly arranged metal nodes, which are not limited to specific facets, the cooperative electrocatalytic mechanism during the faradaic WOR process is investigated through operando Raman spectroscopy and density functional theory calculations. These results enable the interpretation of the electrochemical WOR mechanism based on MOF, providing a further fundamental understanding of electrocatalytic activity in bimetallic systems.

A novel GO hoisted SnO2-BiOBr bifunctional catalyst for the remediation of organic dyes under illumination by visible light and electrocatalytic water splitting.

It is imperative to develop affordable multi-functional catalysts based on transition metals for various applications, such as dye degradation or the production of green energy. For the first time, we propose a simple chemical bath method to create a SnO2-BiOBr-rGO heterojunction with remarkable photocatalytic and electrocatalytic activities. After introducing graphene oxide (GO) into the SnO2-BiOBr nanocomposite, the charge separation, electron mobility, surface area, and electrochemical properties were significantly improved. The X-ray diffraction results show the successful integration of GO into the SnO2-BiOBr nanocomposite. Systematic material characterization by scanning and transmission electron microscopy showed that the photocatalysts are composed of uniformly distributed SnO2 nanoparticles (∼11 nm) on the regular nanosheets of BiOBr (∼94 nm) and rGO. The SnO2-BiOBr-rGO photocatalyst has outstanding photocatalytic activity when it comes to reducing a variety of organic dyes like rhodamine B (RhB) and methylene blue (MB). Within 90 minutes of visible light illumination, degradation of a maximum of 99% for MB and 99.8% for RhB was noted. The oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) performance was also tested for the ternary nanocomposite, and significantly lower overpotential values of 0.34 and -0.11 V (vs. RHE) at 10 mA cm-2 were observed for the OER and HER, respectively. Furthermore, the Tafel slope values are 34 and 39 mV dec-1 for the OER and HER, respectively. The catalytic degradation of dyes with visible light and efficient OER and HER performance offer this work a broad spectrum of potential applications.

Hydrodynamics-Controlled Single-Particle Electrocatalysis.

Electrocatalysis is considered promising in renewable energy conversion and storage, yet numerous efforts rely on catalyst design to advance catalytic activity. Herein, a hydrodynamic single-particle electrocatalysis methodology is developed by integrating collision electrochemistry and microfluidics to improve the activity of an electrocatalysis system. As a proof-of-concept, hydrogen evolution reaction (HER) is electrocatalyzed by individual palladium nanoparticles (Pd NPs), with the development of microchannel-based ultramicroelectrodes. The controlled laminar flow enables the precise delivery of Pd NPs to the electrode-electrolyte interface one by one. Compared to the diffusion condition, hydrodynamic collision improves the number of active sites on a given electrode by 2 orders of magnitude. Furthermore, forced convection enables the enhancement of proton mass transport, thereby increasing the electrocatalytic activity of each single Pd NP. It turns out that the improvement in mass transport increases the reaction rate of HER at individual Pd NPs, thus a phase transition without requiring a high overpotential. This study provides new avenues for enhancing electrocatalytic activity by altering operating conditions, beyond material design limitations.

Explosive Leidenfrost-Droplet-Mediated Synthesis of Monodispersed High-Entropy-Alloy Nanoparticles for Electrocatalysis.

High-entropy-alloy nanoparticles (HEA NPs) exhibit promising potential in various catalytic applications, yet a robust synthesis strategy has been elusive. Here, we introduce a straightforward and universal method, involving the microexplosion of Leidenfrost droplets housing carbon black and metal salt precursors, to fabricate PtRhPdIrRu HEA NPs with a size of ∼2.3 nm. The accumulated pressure within the Leidenfrost droplet triggers an intense explosion within milliseconds, propelling the carbon support and metal salt rapidly into the hot solvent through explosive force. The exceptionally quick temperature rise ensures the coreduction of metal salts, and the dilute local concentration of metal ions limits the final size of the HEA NPs. Additionally, the explosion process can be fine-tuned by selecting different solvents, enabling the harvesting of diverse HEA NPs with superior electrocatalytic activity for alcohol electrooxidation and hydrogen electrocatalysis compared to commercial Pt (Pd) unitary catalysts.

Modulating the D-π-A Interactions in Metal-Covalent Organic Frameworks for Efficient Electroreduction of CO2 into Formate.

Crystalline porous framework materials have attracted tremendous interest in electrocatalytic CO2 reduction owing to their ordered structures and high specific surface areas as well as rich designability, however, still suffer from a lack of accuracy in regulating the binding strength between the catalytic sites and intermediates, which is crucial for optimizing the electrocatalytic activity and expanding the product types. Herein, we report three new kinds of vinylene-linked metal-covalent organic frameworks (TMT-CH3-MCOF, TMP-CH3-MCOF and TMP-MCOF) with continuously tunable D-π-A interactions by adjusting the structure of the monomers at the molecular level for realizing efficient electroreduction of CO2 to formate for the first time. Interestingly, compared with TMT-CH3-MCOF and TMP-MCOF, the TMP-CH3-MCOF exhibited the highest HCOO- Faradaic efficiency (FEHCOO-) of 95.6% at -1.0 V vs RHE and displayed the FEHCOO- above 90% at the voltage range of -1.0 to -1.2 V vs. RHE, which is one of the highest among various kinds of reported electrocatalysts. Theoretical calculations further reveal that the catalytic sites in TMP-CH3-MCOF with unique moderate D-π-A interactions have suitable binding ability towards the reaction intermediate, which is beneficial for the formation of *HCOO and desorption of *HCOOH, thus effectively promoting the electroreduction of CO2 to formate.

Electrodeposited Phosphorous-Doped Graphitic Carbon Nitride as A Versatile Metal Free Interface for Tryptophan Detection in Dietary, Nutritional, and Clinical Samples

Tryptophan (TRP) is an essential amino acid that is crucial for human growth and must be obtained through a dietary source or nutritional supplements. Both, the overconsumption or deficiency induces clinical symptoms. Therefore, a sensitive and selective method for quantifying TRP in dietary products, nutritional supplements, and clinical samples is essential. In this work, we have electrodeposited phosphorous doped graphitic carbon nitride (P-gCN) for developing a TRP voltammetric sensor. Outlining the benefits of electrodeposition over drop-casting, the developed P-gCN | GCE sensor demonstrated 7.83 times more sensitivity and a negative shift of ∼0.10 V for TRP electro-oxidation compared to unmodified electrode implying its remarkable electrocatalytic activity. The sensor featured a detection-limit of 7.1 nM and showcased excellent stability, repeatability and reproducibility. The practical utility of the sensor was manifested by estimating TRP in over 12 real samples including, food products, nutritional supplements and clinical samples (urine and human blood serum).

Modulating the D‐π‐A Interactions in Metal‐Covalent Organic Frameworks for Efficient Electroreduction of CO2 into Formate

Crystalline porous framework materials have attracted tremendous interest in electrocatalytic CO2 reduction owing to their ordered structures and high specific surface areas as well as rich designability, however, still suffer from a lack of accuracy in regulating the binding strength between the catalytic sites and intermediates, which is crucial for optimizing the electrocatalytic activity and expanding the product types. Herein, we report three new kinds of vinylene‐linked metal‐covalent organic frameworks (TMT‐CH3‐MCOF, TMP‐CH3‐MCOF and TMP‐MCOF) with continuously tunable D‐π‐A interactions by adjusting the structure of the monomers at the molecular level for realizing efficient electroreduction of CO2 to formate for the first time. Interestingly, compared with TMT‐CH3‐MCOF and TMP‐MCOF, the TMP‐CH3‐MCOF exhibited the highest HCOO‐ Faradaic efficiency (FEHCOO‐) of 95.6% at ‐1.0 V vs RHE and displayed the FEHCOO‐ above 90% at the voltage range of ‐1.0 to ‐1.2 V vs. RHE, which is one of the highest among various kinds of reported electrocatalysts. Theoretical calculations further reveal that the catalytic sites in TMP‐CH3‐MCOF with unique moderate D‐π‐A interactions have suitable binding ability towards the reaction intermediate, which is beneficial for the formation of *HCOO and desorption of *HCOOH, thus effectively promoting the electroreduction of CO2 to formate.