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1.
J Colloid Interface Sci ; 677(Pt B): 853-861, 2025 Jan.
Article in English | MEDLINE | ID: mdl-39173517

ABSTRACT

Electrocatalytic nitrate reduction reaction presents a promising avenue for environmentally friendly ammonia (NH3) synthesis and wastewater treatment. An essential aspect to consider is the meticulous design of electrocatalysts. This study explores the utilization of a Ni-Co alloy nanosheet-decorated three-dimensional titanium dioxide (3D-TiO2) nanobelts electrodeposited on titanium meshes (NixCoy@TiO2/TM) for efficient electrocatalytic NH3 production. The optimized Ni1Co3@TiO2/TM electrode achieves a significant NH3 yield of 676.3 ± 27.1 umol h-1 cm-2 with an impressive Faradaic efficiency (FE) of 95.1 % ± 2.1 % in a 0.1 M KOH solution containing 0.1 M NO3- at -0.4 V versus the reversible hydrogen electrode. Additionally, the electrode demonstrates exceptional electrochemical activity for NH3 synthesis in simulated wastewater, delivering an outstanding NH3 yield of 751.6 ± 44.3 umol h-1 cm-2 with a FE of 96.8 % ± 0.4 % at the same potential of -0.4 V. Moreover, the electrode exhibits minimal variation in current density, NH3 yields and FEs throughout the 24-h stability test and the 20-cycle test, demonstrating its excellent stability and durability. This study offers a straightforward electrodeposited approach for the development of 3D-nanostructured alloys as catalysts for NH3 electrosynthesis from nitrates at room temperature.

2.
J Colloid Interface Sci ; 677(Pt B): 1005-1013, 2025 Jan.
Article in English | MEDLINE | ID: mdl-39178664

ABSTRACT

Electrochemical water splitting for hydrogen production is an ideal process for clean energy production. However, highly active and low-cost electrocatalysts are essential and challenging. In this work, a multi-component Cu-based catalyst (Ru-M-C-Cu), synergized with ruthenium (Ru) heteroatom doping, was synthesized via a facile immersion-calcination-immersion method. Based on the cotton biomass substrate, a hollow tubular structure was obtained. By virtue of its distinctive structure and high carbon content, cotton biomass assumed a dual role as a sacrificial template and a reducing agent in the eco-friendly synthesis of electrocatalysts, which was instrumental in the creation of a multi-component system augmented by heteroatom doping. The multi-component system was constructed by in-situ transformation and redox reaction during calcination in an oxygen-free environment. The Ru-M-C-Cu catalyst exhibited a competitive overpotential of 108 mV at a current density of 10 mA cm-2 for alkaline hydrogen evolution reaction (HER). The satisfactory catalytic performance of Ru-M-C-Cu can be attributed to the fact that the Ru-O-Cu catalytic centers enhanced the adsorption and desorption abilities of the Cu-O active sites toward hydrogen. Furthermore, the hollow tubular structure allowed the electrolyte to make full contact with the active sites of the Ru-M-C-Cu catalyst, thus accelerated the HER kinetics. The catalyst showed structural and chemical stability after a 12-hour successive test. Besides, the production cost of Ru-M-C-Cu was significantly reduced by 99.1 % than that of commercial 20 % Pt/C, showing the potential as an alternative catalyst by offering a more accessible and sustainable source. This work provides a new design of sustainable low-budget electrocatalysts with the proposed strategies expected for producing clean and renewable hydrogen energy.

3.
J Colloid Interface Sci ; 677(Pt B): 904-921, 2025 Jan.
Article in English | MEDLINE | ID: mdl-39178670

ABSTRACT

It is a challenging task to design and synthesize stable, and high-performance non-precious metals bifunctional catalysts for water-splitting. Herein, the coupling between Se vacancy and interface engineering is highlighted to synthesize a unique CoFeSe hollow nanocubes structure on MXene-modified nickel foam (NF) by in-situ phase transition from bifunctionality prussian blue analogue (PBA) derivatives (VSe-CoFeSe@MXene/NF). DFT theory reveals that the Se vacancy and interface engineering modulate the surface electronic structure and optimize the surface adsorption energy of the intermediates. Experimental data also confirm that the as-prepared CoFeSe@MF catalyst exhibits advanced electrocatalytic properties, 283 mV (OER) and 67 mV (HER) are required to drive the current density of 10 mA cm-2. Notably, it is assembled into a two-electrode system for integral water decomposition, which only requires a low cell potential of 1.57 V at current of 10 mA cm-2, together with excellent durability for 48 h. The strategy is expected to provide a new direction for the design and construction of highly efficient collaborative integrated water decomposition electrocatalysts.

4.
J Colloid Interface Sci ; 677(Pt A): 140-149, 2025 Jan.
Article in English | MEDLINE | ID: mdl-39083891

ABSTRACT

Multinary metal sulfides (MMSs) are highly suitable candidates for the application of electrocatalysis as they offer numerous parameters for optimizing the electronic structure and catalytic sites. Herein, a stable nanoarchitecture consisting of MMSs ((NiCoCrMnFe)Sx) nanoparticles embedded in S, N-codoped carbon (SNC) layers derived from metal organic framework (MOF) and supported on carbonized wood fibers (CWF) was fabricated by directly carbonization. Benefiting from this carbon-coated configuration, along with the synergistic effects within multinary metal systems, (NiCoCrMnFe)Sx@SNC/CWF delivers an exceptionally low overpotential of 260 mV at a high current density of 1000 mA cm-2, a small Tafel slope of 48.5 mV dec-1, and robust electrocatalytic stability. Furthermore, the (NiCoCrMnFe)Sx@SNC/CWF used as the cathode of rechargeable Zn-air batteries demonstrates higher power density and remarkable durability, surpassing that of commercial RuO2. Thus, we showcase the feasibility and advantages of employing highly efficient and durable MMSs materials for low-cost and sustainable energy conversion.

5.
J Colloid Interface Sci ; 677(Pt A): 587-598, 2025 Jan.
Article in English | MEDLINE | ID: mdl-39116558

ABSTRACT

Electrochemical water splitting has been considered as a key pathway to generate environmentally friendly green hydrogen energy and it is essential to design highly efficient electrocatalysts at affordable cost to facilitate the redox reactions of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). In this work, a novel micro-clustered Ru/CuMnBP electrocatalyst is introduced, prepared via hydrothermal deposition and soaking-assisted Ru doping approaches on Ni foam substrate. Ru/CuMnBP micro-clusters exhibit relatively low HER/OER turnover overpotentials of 11 mV and 85 mV at 10 mA/cm2 in 1 M KOH. It also demonstrates a low 2-E turnover cell voltage of 1.53 V at 10 mA/cm2 for the overall water-splitting, which is comparable with the benchmark electrodes of Pt/C||RuO2. At a super high-current density of 2000 mA/cm2, the dual functional Ru/CuMnBP demonstrates an exceptionally low 2-E cell voltage of 3.13 V and also exhibits superior stability for over 10 h in 1 M KOH. Excellent electrochemical performances originate from the large electrochemical active surface area with the micro cluster morphology, high intrinsic activity of CuMnBP micro-clusters optimized through component ratio adjustment and the beneficial Ru doping effect, which enhances active site density, conductivity and stability. The usage of Ru in small quantities via the simple soaking doping approach significantly improves electrochemical reaction rates for both HER and OER, making Ru/CuMnBP micro-clusters promising candidates for advanced electrocatalytic applications.

6.
J Colloid Interface Sci ; 677(Pt A): 677-686, 2025 Jan.
Article in English | MEDLINE | ID: mdl-39116565

ABSTRACT

Developing carbon-supported Pt-based electrocatalysts with high activity and long-durability for the oxygen reduction reaction (ORR) is an enormous challenge for their commercial applications due to the corrosion of carbon supports in acid/alkaline solution at high potential. In this work, a Janus structural TaON/graphene-like carbon (GLC) was synthesized via an in-situ molecular selfassembly strategy, which was used as a dual-carrier for platinum (Pt). The as-obtained Pt/TaON/GLC presents high half-wave potential (0.94 V vs. RHE), excellent mass (1.48 A mgPt-1) and specific (1.75 mA cmPt-2) activities at 0.9 V, and superior long-term durability with a minimal loss (8.0 %) of mass activity after 10,000 cycles in alkaline solution, outperforming those of Pt/C and other catalysts. The structural characterizations and density functional theory (DFT) calculations indicate that the Pt/TaON/GLC catalyst exhibits the maximum synergies, including enhanced interfacial electron density, improved charge transfer, enhanced O2 adsorption, andsuperimposed OO cleavage. This work shows a potential strategy for preparing the high-active and long-durable Pt-based electrocatalyst by synergism-promoted interface engineering.

7.
J Colloid Interface Sci ; 677(Pt A): 771-780, 2025 Jan.
Article in English | MEDLINE | ID: mdl-39121661

ABSTRACT

Oxygen reduction reaction (ORR) serves as the foundation for various electrochemical energy storage devices. Fe/NC catalysts are expected to replace commercial Pt/C as oxygen electrode catalysts based on the structural tunability at the atomic level, abundant iron ore reserves and excellent activity. Nevertheless, the lack of durability and low active site density impede its advancement. In this work, a durable catalyst, CuFe/NC, for ORR was prepared by modulating the interfacial composition and electronic structure. The introduction of Cu nanoclusters partially eliminates the Fenton effect from Fe and optimizes the electron structure of FeNx, thereby effectively enhancing the long-term durability and activity. The prepared CuFe/NC exhibits a half-wave potential (E1/2) of 0.90 V and superior stability with a decrease in E1/2 of only 20 mV after 10,000 cycles. The assembled alkaline Zinc-Air batteries (ZABs) with CuFe/NC exhibit an open-circuit potential of 1.458 V. At a current density of 5 mA cm-2, the batteries are capable of operation for 600 h with a stable polarization. This CuFe/NC may promote the practical application of novel and renewable electrochemical energy storage devices.

8.
J Colloid Interface Sci ; 677(Pt A): 974-982, 2025 Jan.
Article in English | MEDLINE | ID: mdl-39128291

ABSTRACT

Heterostructures and the introduction of heterogeneous elements have been regarded as effective strategies to promote electrochemical performance. Herein, sulfur species are introduced by a simple hydrothermal vulcanization method, which constructs the open heterostructure Fe7S8/Mn(OH)2 as a bifunctional material. The open cordyceps-like morphology can make the material contact more sufficiently with the electrolyte, exposing a large number of reaction sites. Furthermore, the introduction of the heterogeneous element S successfully constructs a heterogeneous interface, the interface-modulated composite material consists of Mn atoms contributing the main density of states (DOS) near the Fermi energy level from the density functional theory (DFT) calculations, which optimizes the adsorption energy of oxygen-containing intermediates during the oxygen evolution reaction (OER) process and reduces the reaction energy barrier, being conducive to the improvement of the material's electrochemical properties. As predicted, the Fe7S8/Mn(OH)2 material exhibits remarkable electrochemical properties, such as an overpotential of 202 mV at 10 mA cm-2 for the oxygen evolution reaction and even a specific capacitance of 2198 F g-1 at 1 A g-1. This work provides new insights into the role of introducing sulfur species and controlling the structure of the material, and exemplifies novel design ideas for developing bifunctional materials for energy storage and conversion.

9.
Small ; : e2407196, 2024 Oct 10.
Article in English | MEDLINE | ID: mdl-39385656

ABSTRACT

The rational design of polysulfide electrocatalysts is of vital importance to achieve longevous Li─S batteries. Notwithstanding fruitful advances made in elevating electrocatalytic activity, efforts to regulate precatalyst phase evolution and protect active sites are still lacking. Herein, an in situ graphene-encapsulated bimetallic model catalyst (CoNi@G) is developed for striking a balance between electrocatalytic activity and stability for sulfur electrochemistry. The layer numbers of directly grown graphene can be dictated by tuning the synthetic duration. Exhaustive experimental and theoretical analysis comprehensively reveals that the tailored graphene chainmail boosts catalytic durability while guaranteeing moderate phase evolution, accordingly attaining a decorated surface sulfidation with advanced catalytic essence. Benefiting from the sustainable polysulfide electrocatalysis, CoNi@G enabled sulfur electrodes to harvest a capacity output of 1276.2 mAh g-1 at 0.2 C and a negligible capacity decay of 0.055% per cycle after 1000 cycles at 1.0 C. Such a maneuver can be readily extended to other metallic catalysts including NiFe, CoFe, or Co. The work elucidates the precatalyst phase evolution mechanism through a controllable graphene-armored strategy, offering meaningful guidance to realize durable electrocatalysts in Li─S batteries.

10.
J Colloid Interface Sci ; 679(Pt A): 487-495, 2024 Oct 03.
Article in English | MEDLINE | ID: mdl-39374558

ABSTRACT

The development of cost-effective, highly active, and stable electrocatalysts for water splitting to produce green hydrogen is crucial for advancing clean and sustainable energy technologies. Herein, we present an innovative in-situ synthesis of FeOOH nanorods@NiOOH nanosheets on nickel foam (FeOOH@NiOOH/NF) at an unprecedentedly low temperature, resulting in a highly efficient electrocatalyst for overall water splitting. The optimized FeOOH@NiOOH/NF sample, evaluated through time-dependent studies, exhibits exceptional oxygen evolution reaction (OER) performance with a low overpotential of 261 mV at a current density of 20 mA cm-2, alongside outstanding hydrogen evolution reaction (HER) activity with an overpotential of 150 mV at a current density of 10 mA cm-2, demonstrating excellent stability in alkaline solution. The water-splitting device featuring FeOOH@NiOOH/NF-2 electrodes achieves a voltage of 1.59 V at a current density of 10 mA cm-2, rivalling the state-of-the-art RuO2/NF||PtC/NF electrode system. Density functional theory (DFT) calculations unveil the efficient functionality of the Fe sites within the FeOOH@NiOOH heterojunction as the active OER catalyst, while the Ni centres are identified as the active HER sites. The enhanced performance of OER and HER is attributed to the tailored electronic structure at the heterojunction, modified magnetic moments of active sites, and increased electron density in the dx2-y2 orbital of Fe. This work provides critical insights into the rational design of advanced electrocatalysts for efficient water splitting.

11.
Angew Chem Int Ed Engl ; : e202415216, 2024 Oct 06.
Article in English | MEDLINE | ID: mdl-39370547

ABSTRACT

The development of advanced bifunctional catalysts for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is significant for rechargeable zinc-air batteries (ZABs). Herein, a unique dual active center alloying strategy is proposed to achieve the efficient bifunctional oxygen catalysis, and the high entropy effect is further exploited to modulate the structure and performance of the catalysts. The MOF-assisted pyrolysis-replacement-alloying method was employed to construct the CoCuFeAgRu high-entropy alloy (HEA), which are uniformly anchored in porous nitrogen-doped carbon nanosheets. Notably, the obtained HEA catalyst exhibits excellent catalytic performance for both ORR and OER, and a peak power density of 136. 53 mW cm-2 and an energy density of 987.9 mAh gZn-1, surpassing the most of the previously reported bifunctional oxygen electrocatalysts. Moreover, the assembled flexible rechargeable ZAB enables excellent performance even at the ultralow temperature of -40°C, with an energy density of 601.6 mAh gZn-1 and remarkable cycling stability up to 1,650 hours. Combined experimental and theoretical calculation results reveal that the excellent bifunctional catalytic activity of the HEA catalyst originated from the synergistic effect of the Ag and Ru dual active centers, and the optimization of the electronic structure by alloying effect.

12.
Small ; : e2407495, 2024 Sep 30.
Article in English | MEDLINE | ID: mdl-39350444

ABSTRACT

The rational design of pH-universal electrocatalyst with high-efficiency, low-cost and large current output suitable for industrial hydrogen evolution reaction (HER) is crucial for hydrogen production via water splitting. Herein, phase engineering of ruthenium (Ru) electrocatalyst comprised of metastable unconventional face-centered cubic (fcc) and conventional hexagonal close-packed (hcp) crystalline phase supported on nitrogen-doped carbon matrix (fcc/hcp-Ru/NC) is successfully synthesized through a facile pyrolysis approach. Fascinatingly, the fcc/hcp-Ru/NC displayed excellent electrocatalytic HER performance under a universal pH range. To deliver a current density of 10 mA cm-2, the fcc/hcp-Ru/NC required overpotentials of 16.8, 23.8 and 22.3 mV in 1 M KOH, 0.5 M H2SO4 and 1 M phosphate buffered solution (PBS), respectively. Even to drive an industrial-level current density of 500 and 1000 mA cm-2, the corresponding overpotentials are 189.8 and 284 mV in alkaline, 202 and 287 mV in acidic media, respectively. Experimental and theoretical calculation result unveiled that the charge migration from fcc-Ru to hcp-Ru induced by work function discrepancy within fcc/hcp-Ru/NC regulate the d-band center of Ru sites, which facilitated the water adsorption and dissociation, thus boosting the electrocatalytic HER performance. The present work paves the way for construction of novel and efficient electrocatalysts for energy conversion and storage.

13.
Environ Sci Technol ; 2024 Oct 01.
Article in English | MEDLINE | ID: mdl-39351847

ABSTRACT

Water electrolysis for green H2 production traditionally requires a stable supply of renewable electricity and pure water. However, spatial separation of renewables and water resources as well as water scarcity per capita in China necessitate unconventional water resources for electrolysis. Reclaimed water produced from municipal wastewater treatment plants is widely distributed with quality improved significantly in recent years, which may be a promising alternative to feedstock. However, there are few reports on the direct use of this wastewater for H2 production. Here, we present a direct electrolysis of reclaimed water for decentralized H2 production by developing a highly efficient and stable bifunctional 3D-dandelion-like (DL) vanadium(V)-doped CoP catalyst grown in situ on Ni foam (NF) in an alkaline electrolyzer. The V-CoP-DL/NF electrode decreases 6.5 and 25% overpotentials of the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively, compared to noble-metal Pt (HER) and IrO2 (OER) catalysts, and exhibits exceptional durability, as a voltage required for overall reclaimed water splitting only increases by 80 mV (1.81-1.89 V) after 90 days of operation at a current density of 10 mA cm-2. The maximum stable current can reach 1000 mA cm-2. The impacts of potential pollutants in reclaimed water on the performance of electrolysis and the behavior of major wastewater ions in alkaline electrolyte were investigated. The observed exceptional performance is attributed to the catalyst's unique nanostructure, which enhances charge transfer and reactant/electrolyte diffusion. The in situ growth strategy further enhances the conductivity and stability of the catalyst. This work underscores the feasibility of utilizing reclaimed water instead of pure water as the feedstock for sustainable hydrogen production.

14.
J Colloid Interface Sci ; 678(Pt C): 968-976, 2024 Sep 21.
Article in English | MEDLINE | ID: mdl-39326168

ABSTRACT

The development of sustainable energy technologies relies on the exploitation of efficient and durable electrocatalysts for water splitting at high current densities. Our work presents a novel bifunctional catalyst, denoted as NM@NC/CC, which combines the benefits of NiSe2-MoSe2 heterojunctions with nitrogen-enriched porous carbon derived from metal-organic frameworks (MOFs). The integration of these components is designed to harness their combined advantages, which include enhanced electron transfer, improved mass and gas evolution dynamics, and an increased number of catalytically active sites. These features collectively optimize the energetics for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). As a result, the catalyst facilitates rapid kinetics for the overall water-splitting process. The NM@NC/CC demonstrates low overpotentials, requiring only 91 mV for the HER and 280 mV for the OER to reach a current density of 10 mA cm-2. Even at higher current densities of 100 mA cm-2 for HER and 50 mA cm-2 for OER, the overpotentials are only 159 mV and 350 mV, respectively. Additionally, a two-electrode setup using this catalyst achieves a current density of 10 mA cm-2 with a minimal cell voltage of 1.56 V. The insights gained from this study will contribute to the advancement of electrocatalysts for energy conversion technologies.

15.
ACS Nano ; 18(40): 27804-27816, 2024 Oct 08.
Article in English | MEDLINE | ID: mdl-39348091

ABSTRACT

High-entropy perovskite oxides, in which the B-type metal site of perovskite oxides (ABO3) is occupied by over five kinds of transition metal ions, show promising applications in energy storage and conversion fields. Herein, high-entropy perovskite oxides (LaSr(5TM)O3) composed of Cr, Mn, Fe, Co, and Ni at the B-type metal site are prepared as oxygen electrocatalysts for Li-O2 batteries. The presence of compressive strain in LaSr(5TM)O3 effectively regulates the 3d orbit occupancy of the active Co site (Co2+ → Co3+) and lifts the energy level of the Co d-band center, thus leading to enhanced adsorption toward the LiO2 intermediate on Co sites. Furthermore, the high electron-drawing capability of Cr sites ensures sufficient electron exchange and further strengthens the adsorption of LiO2. As expected, the Li-O2 battery with a LaSr(5TM)O3 electrode delivers a low overpotential (0.79 V) and superior cyclability (226 cycles). This study provides a meaningful strain strategy to improve the electrocatalytic activity of multicomponent oxides via fabricating high-entropy materials.

16.
ACS Appl Mater Interfaces ; 16(39): 52406-52413, 2024 Oct 02.
Article in English | MEDLINE | ID: mdl-39299221

ABSTRACT

The synthesis of bimetallic and trimetallic platinum-based octahedral catalysts for the cathode of proton exchange membrane fuel cells (PEMFCs) is a particularly active area aimed at meeting technological requirements in terms of durability and cost. The electrocatalytic activity and stability of these shaped catalysts were tested at relatively high potentials (@0.9 V vs RHE) and at lower current densities using the rotating disk electrode, which is less suitable for assessing their behavior under the operating conditions of PEMFCs. In this work, we use a gas diffusion electrode (GDE) half-cell setup to test the performance of the catalysts under application-oriented conditions, relatively higher current densities, and a square-wave stability test. After the stability test, we analyzed the GDE catalytic layer to study the agglomeration and dissolution of the transition metal under these conditions by using high-resolution scanning electron microscopy and energy-dispersive X-ray spectroscopy. The present results provide valuable guidance for developing next-generation active and durable catalysts for PEMFCs.

17.
Biosensors (Basel) ; 14(9)2024 Aug 24.
Article in English | MEDLINE | ID: mdl-39329787

ABSTRACT

Our research addresses the pressing need for environmental sensors capable of large-scale, on-site detection of a wide array of heavy metals with highly accurate sensor metrics. We present a novel approach using electrochemically polished (ECP) carbon screen-printed electrodes (cSPEs) for high-sensitivity detection of cadmium and lead. By applying a range of techniques, including scanning electron microscopy, energy-dispersive spectroscopy, Raman spectroscopy, electrochemical impedance spectroscopy, and cyclic voltammetry, we investigated the impact of the electrochemical potential scan range, scan rate, and the number of cycles on electrode response and its ability to detect cadmium and lead. Our findings reveal a 41 ± 1.2% increase in voltammogram currents and a 51 ± 1.6% decrease in potential separations (n = 3), indicating a significantly improved active electrode area and kinetics. The impedance model elucidates the microstructural and electrochemical property changes in the ECP-treated electrodes, showing an 88 ± 2% (n = 3) decrease in the charge transfer resistance, leading to enhanced electrode electrical conductivity. A bismuth-reduced graphene oxide nanocomposite-modified, ECP-treated electrode demonstrated a higher cadmium and lead sensitivity of up to 5 ± 0.1 µAppb-1cm-2 and 2.7 ± 0.1 µAppb-1cm-2 (n = 3), respectively, resulting in sub-ppb limits of detection in spiked deionized water samples. Our study underscores the potential of optimally ECP-activated electrodes as a foundation for designing ultrasensitive heavy metal sensors for a wide range of real-world heavy metal-contaminated waters.


Subject(s)
Cadmium , Carbon , Electrochemical Techniques , Electrodes , Graphite , Metals, Heavy , Metals, Heavy/analysis , Carbon/chemistry , Graphite/chemistry , Cadmium/analysis , Lead/analysis , Biosensing Techniques , Dielectric Spectroscopy , Bismuth/chemistry , Spectrum Analysis, Raman
18.
Gels ; 10(9)2024 Aug 28.
Article in English | MEDLINE | ID: mdl-39330160

ABSTRACT

Developing lightweight, highly active surfaces with a high level of performance and great stability is crucial for ensuring the dependability of energy harvesting and conversion devices. Aerogel-based electrocatalysts are an efficient option for electrocatalytic hydrogen production because of their numerous benefits, such as their compatibility with interface engineering and their porous architecture. Herein, we report on the facile synthesis of a nanorod-like molybdenum sulfide-reduced graphene oxide (M-rG) aerogel as an electrocatalyst for the hydrogen evolution reaction (HER). The 3D architecture of the network-like structure of the M-rG hybrid aerogel was created via the hydrothermal technique, using a saturated NaCl solution-assisted process, where the MoS2 was homogeneously incorporated within the interconnected rGO aerogel. The optimized M-rG-300 aerogel electrocatalyst had a significantly decreased overpotential of 112 mV at 10 mA/cm2 for the HER in alkaline conditions. The M-rG-300 also showed a higher level of reliability. The remarkable efficiency of the HER involving the M-rG-300 is principally attributed to the excellent connectivity between the rGO and MoS2 in the aerogel structure. The efficient interconnection influenced the achievement of a larger electrochemically active surface area, increased electrical conductivity, and the exposure of more active sites for the HER. Furthermore, the creation of a synergistic effect in the M-rG-300 aerogel is the most probable mechanism to boost the electrocatalytic activity.

19.
Nanomaterials (Basel) ; 14(18)2024 Sep 18.
Article in English | MEDLINE | ID: mdl-39330671

ABSTRACT

This study aims to explore the n-FeO and p-α-Fe2O3 semiconductor nanoparticles in hydrogen (HER) and oxygen (OER) evolution reactions and a combined full cell electrocatalyst system to electrolyze the water. We have observed a distinct electrocatalytic performance for both HER and OER by tuning the interplay between iron oxidation states Fe2+ and Fe3+ and utilizing phase-transformed iron oxide nanoparticles (NPs). The Fe2+ rich n-FeO NPs exhibited superior HER performance compared to p-α-Fe2O3 and Fe(OH)x NPs, which is attributed to the enhancement in n-type semiconducting nature under HER potential, facilitating the electron transfer for the reduction in H+ ions. In contrast, p-α-Fe2O3 NPs demonstrated excellent OER activity. An H-cell constructed using n-FeO||p-α-Fe2O3 NPs as cathode and anode achieved a cell voltage of 1.87 V at a current density of 50 mA/cm2. The cell exhibited remarkable stability after 30 h of activation and maintained the high current density of 100 mA/cm2 for 80 h with a negligible increase in cell voltage. This work highlights the semiconducting properties of n-FeO and p-α-Fe2O3 for the electrochemical water splitting system using the band bending phenomenon under the applied potential.

20.
J Colloid Interface Sci ; 678(Pt C): 1087-1095, 2024 Sep 21.
Article in English | MEDLINE | ID: mdl-39341140

ABSTRACT

Developing an efficient, robust, and noble metal-free electrocatalyst that can catalyse oxygen evolution reactions (OER) remains a significant challenge. CoS2, a representative of pyrite form transition metal dichalcogenides, has recently been identified as an economical catalyst. Here, an incredibly quick and scalable technique for novel catalysts synthesized with the use of the microwave method was introduced. Manganese-doped cobalt sulphide (Mn-CoS2) showed outstanding OER with a very low overpotential of 227 mV at 10 mA cm-2. Exposure of surface atoms resulted in high electrochemical activity, where the defects facilitated charge and mass transfer along the nanostructure, allowing surface dependent electrochemical reactions to be performed more efficiently. The electronic properties of pristine and transition-metal-doped CoS2 structures were also investigated using density functional theory (DFT). To better understand transition metal's dependent impact on crystal structure, orbital electronic participation, charge density, and charge transformation in both pristine and Mn-dopedCoS2 frameworks were calculated and analysized. Our synthesis approach is primarily commercial and extensible, overcoming synthesis challenge of transition metal sulphide nanostructures with prime quality and implying a potential for commercial uses.

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