Efficient Electrocatalysts Research Articles

Effect of Sm dopant on electrocatalytic activity of AgNbO3 perovskite fabricated by sonication method for Oxygen Evaluation Reaction (OER)

Excessive reliance on fossil fuels causes a variety of difficulties and the use of efficient electrocatalysts material has exhibited significant attention for high electrocatalytic activity. Most transition metal oxide materials performance can be enhanced by the incorporation of metals for OER activity. This work presents the synthesis of samarium (Sm) doped silver niobium oxide (AgNbO3) was achieved using sonication techniques. An electrocatalyst, Sm-doped AgNbO3, has shown promising results for oxygen evolution reaction (OER) in alkaline medium with a significant increase in active sites, enhanced electrical conductivity and improved stability. The Sm-doped AgNbO3 electrocatalyst exhibits overpotential of 203 mV and Tafel slope of 35.22 mV dec−1 for OER activity at current densities of 10 mA cm−2. By utilizing, electrochemical surface area (ECSA), the Sm-doped AgNbO3 electrocatalyst exhibited higher ECSA values of 1009 cm−2 with a higher roughness factor of 2008.60. Further, observations of low charge transfer resistance value (Rct = 0.17 Ω) along with a durability of 50 h, indicate that this material is highly efficient and long-lasting as an electrocatalyst for energy conversion systems.

Synthesis of Stable and Efficient Electrocatalysts for Hydrogen Evolution: Hierarchical NiMo-Based Hollow Nanotubes

Large-scale development of low-cost, efficient, and stable powder electrocatalysts for the hydrogen evolution reaction (HER) in alkaline solutions is a key step toward commercial hydrogen production. Herein, a hierarchical NiMo-MoO3-x hollow nanotube (NiMo-MoO3-x-HNT) with bifunctional groups as an efficient HER electrocatalyst was strategically invented using an MoO3 nanorod (MoO3−NR) as the precursor. The synthesis mechanism of the NiMo-MoO3-x-HNT is established based on in-depth investigations using diffraction, spectral, and microscopy results. Experimental results suggest that the NiMo-MoO3-x-HNT exhibits excellent electrocatalytic HER performance in 1 M KOH, with a low overpotential of 26.5 mV@10.0 mA cm-2 and a small Tafel slope of 32.6 mV dec–1. These values are comparable to those of cutting-edge electrocatalysts based on platinum-group metals. Moreover, it exhibits an almost unaffected cyclic stability over 50,000 cycles and robust durability over 98 h. This remarkable performance is attributed to its bifunctional groups and the porous hierarchical hollow nanotubular morphology. In summary, this study proposes a novel, efficient, and cost-effective strategy for the development of noble metal-free, high-performance HER electrocatalysts.

Bimetallic Nitride Ni3Mo3N Microrods with Abundant Catalytic Sites Used as Efficient Electrocatalysts for Hydrogen Evolution Reaction

Abstract The importance of efficient and stable hydrogen evolution reaction (HER) electrocatalysts for hydrogen production in alkaline conditions to energy crisis resolution and environmental pollution is immense. In general, the quantity of catalytic sites in the electrocatalyst limits the current density of HER. In response to such problems, the bimetallic effect of non-noble bimetallic nitrides has been shown to regulate the corresponding catalytic sites. Here, a microrod-like non-noble bimetallic nitride catalyst with Ni3Mo3N microrods uniformly modified on nickel foam was synthesized by hydrothermal and nitriding processes. The catalyst showed high catalytic activity for HER in 1M KOH solution. The overpotential was only 28 mV at a current density of 10 mA·cm-2, demonstrating exceptional electrochemical performance. Furthermore, it exhibited remarkable long-term stability under the same current density. This work will open up a low-cost and simple way for the synthesis of bimetallic nitrides as functional electrode materials for HER and electrochemical detection.

Metal Doping Regulates Electrocatalysts Restructuring during Oxygen Evolution Reaction.

High-efficiency and low-cost catalysts for oxygen evolution reaction (OER) are critical for electrochemical water splitting to generate hydrogen, which is a clean fuel for sustainable energy conversion and storage. Among the emerging OER catalysts, transition metal dichalcogenides have exhibited superior activity compared to commercial standards such as RuO2, but inferior stability due to uncontrolled restructuring with OER. In this study, we create bimetallic sulfide catalysts by adapting the atomic ratio of Ni and Co in CoxNi1-xSy electrocatalysts to investigate the intricate restructuring processes. Surface-sensitive X-ray photoelectron spectroscopy and bulk-sensitive X-ray absorption spectroscopy confirmed the favorable restructuring of transition metal sulfide material following OER processes. Our results indicate that a small amount of Ni substitution can reshape the Co local electronic structure, which regulates the restructuring process to optimize the balance between OER activity and stability. This work represents a significant advancement in the development of efficient and noble metal-free OER electrocatalysts through a doping-regulated restructuring approach.

Charge Redistribution of Lattice-Mismatched Co─Cu3P Boosting pH-Universal Water/Seawater Hydrogen Evolution.

Practical applications of the hydrogen evolution reaction (HER) rely on the development of highly efficient, stable, and low-cost catalysts. Tuning the electronic structure, morphology, and architecture of catalysts is an important way to realize efficient and stable HER electrocatalysts. Herein, Co-doped Cu3P-based sugar-gourd structures (Co─Cu3P/CF) are prepared on copper foam as active electrocatalysts for hydrogen evolution. This hierarchical structure facilitates fast mass transport during electrocatalysis. Notably, the introduction of Co not only induces a charge redistribution but also leads to lattice-mismatch on the atomic scale, which creates defects and performs as additional active sites. Therefore, Co─Cu3P/CF requires an overpotential of only 81, 111, 185, and 230mV to reach currents of 50, 100, 500, and 1000mA cm-2 in alkaline media and remains stable after 10 000 CV cycles in a row and up to 110h i-t stability tests. In addition, it also shows excellent HER performance in water/seawater electrolytes of different pH values. Experimental and DFT show that the introduction of Co modulates the electronic and energy level structures of the catalyst, optimizes the adsorption and desorption behavior of the intermediate, reduces the water dissociation energy barrier during the reaction, accelerates the Volmer step reaction, and thus improves the HER performance.

Metallic Ru─Ru Interaction in Ruthenium Oxide Enabling Durable Proton Exchange Membrane Water Electrolysis.

Developing efficient and robust electrocatalysts toward the oxygen evolution reaction (OER) is critical for proton exchange membrane water electrolysis (PEMWE). RuO2 possesses intrinsically high OER activity, but the concurrent electrochemical dissolution leads to rapid deactivation. Here a unique RuO2 catalyst containing metallic Ru─Ru interactions (m-RuO2) is reported, which maintains stability in practical PEMWE for 100h at 60 °C and 1 A cm-2. Experimental and theoretical investigations suggest that the presence of Ru─Ru interactions significantly increases the energy barrier for the formation of RuO2(OH)2, which is a key intermediate for Ru dissolution, and hence substantially mitigates the electrochemical corrosion of m-RuO2. Meanwhile, the Ru4d band center downshifts, accordingly, ensuring the high OER activity, and the participation of lattice oxygen in the OER is also suppressed at the Ru─Ru sites, further contributing to the enhanced durability. Interestingly, such enhanced stability is also dependent on the size of metallic Ru─Ru cluster, where the energy barrier is further increased for Ru3, but is decreased for Ru5. These results highlight the significance of local coordination structure modulation on the electrochemical stability of RuO2 and open a feasible avenue toward the development of robust OER electrocatalysts for high-performance PEMWE.

Interfacial Engineering of MoS2@CoS2 Heterostructure Electrocatalysts for Effective pH-Universal Hydrogen Evolution Reaction.

The practical utilization of the hydrogen evolution reaction (HER) necessitates the creation of electrocatalysts that are both efficient and abundant in earth elements, capable of operating effectively within a wide pH range. However, this objective continues to present itself as an arduous obstacle. In this research, we propose the incorporation of sulfur vacancies in a novel heterojunction formed by MoS2@CoS2, designed to exhibit remarkable catalytic performances. This efficacy is attributed to the advantageous combination of the low work function and space charge zone at the interface between MoS2 and CoS2 in the heterojunction. The MoS2@CoS2 heterojunction manifests outstanding hydrogen evolution activity over an extensive pH range. Remarkably, achieving a current density of 10 mA cm-2 in aqueous solutions 1.0 M KOH, 0.5 M H2SO4, and 1.0 M phosphate-buffered saline (PBS), respectively, requires only an overpotential of 48, 62, and 164 mV. The Tafel slopes for each case are 43, 32, and 62 mV dec-1, respectively. In this study, the synergistic effect of MoS2 and CoS2 is conducive to electron transfer, making the MoS2@CoS2 heterojunction show excellent electrocatalytic performance. The synergistic effects arising from the heterojunction and sulfur vacancy not only contribute to the observed catalytic prowess but also provide a valuable model and reference for the exploration of other efficient electrocatalysts. This research marks a significant stride toward overcoming the challenges associated with developing electrocatalysts for practical hydrogen evolution applications.

Substantial Electrocatalytic Oxygen Evolution Performances of Activated Carbon-Decorated Vanadium Pentoxide Nanocomposites

Developing the ecofriendly and high-fidelity electrocatalysts for the oxygen evolution reaction (OER) is essential to foster effective production of environmentally friendly hydrogen. Herein, we fabricated the highly efficient OER electrocatalysts of the activated carbon-decorated vanadium pentoxide (AC-V2O5) nanocomposites using a facile hydrothermal technique. The AC-V2O5 nanocomposites displayed an aggregated structure of the AC nano-sheet-anchored orthorhombic V2O5 nanorods. When performing the OER process in an alkaline electrolyte at 10 mA/cm2, AC-V2O5 exhibited the low overpotential (~230 mV), small Tafel slope (~54 mV/dec), and excellent stability. These substantial OER performances of AC-V2O5 could be ascribed to the synergistic effects from both the electrochemically active V2O5 nanorods and the highly conductive AC nanosheets. The results infer that the AC-V2O5 nanocomposites possess a substantial aptitude as a high-performance OER electrocatalyst for production of the future green energy source—hydrogen.

N-doped CoNiOOH with optimized band-structure for photo-assisted electrocatalytic overall seawater splitting

In this work, an efficient and stable photo-assisted electrocatalyst of N-doped CoNiOOH for overall seawater splitting are proposed. The doped N atoms triggered local contractions of lattice, thereby, promoted the morphologies of products to evolve from nanoflowers to nanowires (NWs), and the obvious electrocatalytic enhancements. Especially under the illumination of AM 1.5 G, the U30-NWs exhibited a photo-assisted cathodic current density from −2.0 to −4.0 mA cm−2 at −0.05 V vs RHE, and also an anodic stability for more than 48 hours in seawater. Our studies reveal that the doped N atom could accumulate more electrons than O atom, leading to the degradation of Co and Ni 3d and O 2p states on either side of Fermi level, thus a p-type feature with the widened band gap and improved UV–visible light absorption. Meanwhile, the corrosion resistance was thus improved due to the chemical stable N-Co(Ni)-N bonds. This work provides a practical strategy towards the H2 production via photo-assisted electrocatalytic seawater splitting.

Fabrication of Nanostructured Cu-Au Materials as an Efficient Electrocatalyst for Lactate Determination in Athletes Biological Fluid During Exercise

Fabrication of Nanostructured Cu-Au Materials as an Efficient Electrocatalyst for Lactate Determination in Athletes Biological Fluid During Exercise

Three-dimensional ordered FeTe-SmCoO3 nanocomposite: As efficient electrocatalyst for water oxidation

In this work, FeTe-SmCoO3 is fabricated through a hydrothermal method and then coated on a stainless steel (SS) substrate to enhance the electrocatalytic performance. The crystal structure, surface chemical state, and morphological features of pure (FeTe and SmCoO3) and heterogeneous catalysts (FeTe-SmCoO3) are determined via XRD, XPS, and TEM/EDX techniques. The fabricated FeTe-SmCoO3 electrocatalyst is attributed to the particular morphological design resulting from the synergistic effect of FeTe and SmCoO3 phases. The as-developed high exposure level of active sites with structural transformation greatly promoted the oxidation property with an overpotential only of 199 mV to derive a current density of 10 mA/cm2, also observed a small Tafel slope of 72 mVdec−1 with extraordinary stability of 90 h. The modified heterogeneous catalyst provides outstanding catalytic behavior toward OER in the alkaline solution, due to flexibility and multiple accessible oxidation states of samarium, cobalt, and iron ions. The catalyst not only acquires additional reaction sites and opens up new channels through the dispersion of the metal centers, but also achieves quick electron transfer in FeTe-SmCoO3 nanocomposite through the interconnection between two phases.

Boron-incorporated IrO2-Ta2O5 coating as an efficient electrocatalyst for acidic oxygen evolution reaction

The Ir-based electrocatalysts for the acidic oxygen evolution reaction (OER) have demonstrated remarkable durability. Enhancing the Ir-based electrocatalytic activity still remains crucial owing to the scarcity of iridium. Here, a high-temperature sintering technique is employed to fabricate a boron (B)-incorporated IrO2-Ta2O5 coating with an almost perfect rutile-type crystal structure on a corrosion-resistant titanium substrate, ensuring exceptional stability for the acidic OER. The B-incorporated IrO2-Ta2O5 electrode fabricated in a mixed solution of 0.6 M H3BO3, exhibits an overpotential of 210 mV at a current density of 10 mA cm−2 and a lower Tafel slope of 34.2 mV dec−1 in a 0.5 M H2SO4 solution, which is far lower than the 272 mV overpotential and the 45.3 mV dec−1 of the IrO2-Ta2O5/Ti electrode. The electrode possesses a minimal potential increase even after undergoing continuous OER for 400 h at a high current density of 100 mA cm−2 in a 0.5 M H2SO4 solution. The incorporation of B species into IrO2-Ta2O5 effectively fine-tunes the electronic structure of Ir active sites, leading to a substantial enhancement of the intrinsic electrocatalytic activity. This study provides promising prospects for reducing the energy consumption of noble IrO2-based electrocatalysts in the practical application of electrochemical industry for the acidic OER.

Shape–Preserved CoFeNi–MOF/NF Exhibiting Superior Performance for Overall Water Splitting across Alkaline and Neutral Conditions

This study reported a multi–functional Co0.45Fe0.45Ni0.9–MOF/NF catalyst for oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and overall water splitting, which was synthesized via a novel shape–preserving two–step hydrothermal method. The resulting bowknot flake structure on NF enhanced the exposure of active sites, fostering a superior electrocatalytic surface, and the synergistic effect between Co, Fe, and Ni enhanced the catalytic activity of the active site. In an alkaline environment, the catalyst exhibited impressive overpotentials of 244 mV and 287 mV at current densities of 50 mA cm−2 and 100 mA cm−2, respectively. Transitioning to a neutral environment, an overpotential of 505 mV at a current density of 10 mA cm−2 was achieved with the same catalyst, showing a superior property compared to similar catalysts. Furthermore, it was demonstrated that Co0.45Fe0.45Ni0.9–MOF/NF shows versatility as a bifunctional catalyst, excelling in both OER and HER, as well as overall water splitting. The innovative shape–preserving synthesis method presented in this study offers a facile method to develop an efficient electrocatalyst for OER under both alkaline and neutral conditions, which makes it a promising catalyst for hydrogen production by water splitting.

N/P-doped NiFeV oxide nanosheets with oxygen vacancies as an efficient electrocatalyst for the oxygen evolution reaction.

Plasma treatment as an effective strategy can simultaneously achieve surface modification and heteroatom doping. Here, an N/P-doped NiFeV oxide nanosheet catalyst (N/P-NiFeVO) constructed by Ar/PH3 plasma treatment is used to drive the oxygen evolution reaction (OER). The introduction of V species leads to the formation of an ultrathin ordered nanostructure and exposure of more active sites. Compared to the 2D NiFeV LDH, the prepared N/P-NiFeVO by plasma treatment possesses multiple-valence Fe, V and Ni species, which regulate the intrinsic electronic structure and enable a superior catalytic activity for the OER in alkaline media. Specifically, the N/P-NiFeVO only require an overpotential of 273 mV to drive the current density of 100 mA cm-2. What's more, the electrode can maintain a stable current density in a long-term oxygen evolution reaction (∼120 h) under alkaline conditions. This work provides new insight for the rational design of mixed metal oxides for OER electrocatalysts.

Controlled Synthesis of Bead‐like Pt as an Efficient Electrocatalyst for Electrocatalytic Ammonia Oxidation

AbstractPromoting electrocatalytic ammonia oxidation reaction (AOR) holds the key to develop efficient direct ammonia fuel cells (DAFCs) and ammonia‐mediated hydrogen production (AMHP). Recent investigations indicated that Pt with the exposure of (100) facet has a moderate *N intermediate bonding strength, resulting in the highest AOR electrocatalytic activity among others. Therefore, maximizing the exposure of (100) planes with high active surface area is highly desired for efficient electrocatalysts. In this paper, Pt catalyst composed of directional alignment of nanoparticles around 50 nm (Pt‐100/C) were synthesized by hydrothermal method in the presence of KOH. The KOH concentration was found to modulate the one‐dimensional alignment of nanoparticles. The electrocatalyst showed the largest electrochemically active areas and the highest peak current density (3.14 mA cm−2), and the catalyst exhibited high stability after 500 cycles. A series of electrochemical tests and structural characterizations show that unique bead‐structured Pt combines the excellent activity of nanoparticles with the structural stability of nanowires. A scheme for “exchanging electrodes” has been proposed to solve the problem of catalyst poisoning caused by AOR in AMHP.

Heterogeneous Ni-Boride/Phosphide Anchored Amorphous B-C Layer for Overall Water Electrocatalysis.

The rational design of efficient and economical bifunctional electrocatalysts remained a challenge for overall water electrolysis. In this work, the Ni-boride/ phosphide particles anchored amorphous B-doped carbon layer with hierarchical porous characteristics in Ni foam (Ni3P/Ni3B/B-C/NF) was fabricated for overall water splitting. The Boroncarbide (B4C) power was filled and fixed in the NF interspace through the electroplating and electroless plating, and then annealed in vacuum high temperature. The amorphous B-C layer derived from the B4 C not only speeded up the electron transport, but also cooperate with Ni-boride/phosphide to enhance the electrocatalytic activity for HER and OER synergistically. Furthermore, the hierarchical porous architecture of Ni3P/Ni3B/B-C/NF increased space utilization to load more active materials. The self-supported Ni3P/Ni3B/B-C/NF electrode possessed a low overpotential of 212 and 280 mV to deliver 100 mA cm-2 for HER and OER, respectively, and high stability for 48 h. In particular, the electrolyzer constituted with the Ni3P/Ni3B/B-C/NF bifunctional electrocatalyst only required a voltage of 1.59 V at 50 mA cm-2 for water electrocatalysis under alkaline medium, and demonstrated long-term stability for 48 h. This study provides a new technical path for the development of bifunctional of transition metal borides to promote the application of hydrogen production from water splitting.

RuSe2 and CoSe2 Nanoparticles Incorporated Nitrogen-Doped Carbon as Efficient Trifunctional Electrocatalyst for Zinc-Air Batteries and Water Splitting.

The development of affordable, highly active, and stable trifunctional electrocatalysts is imperative for sustainable energy applications such as overall water splitting and rechargeable Zn-air battery. Herein, we report a composite electrocatalyst with RuSe2 and CoSe2 hybrid nanoparticles embedded in nitrogen-doped carbon (RuSe2CoSe2/NC) synthesized through a carbonization-adsorption-selenylation strategy. This electrocatalyst is a trifunctional electrocatalyst with excellent hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR) activities. An in-depth study of the effect of Se on the electrocatalytic process was conducted. Notably, the incorporation of Se moderately adjusted electronic structure of Ru and Co, enhancing all three types of catalytic performance (HER, η10 = 31 mV; OER, η10 = 248 mV; ORR, E1/2 = 0.834 V) under alkaline condition with accelerated kinetics and improved stability. Density functional theory (DFT) calculation reveals that the (210) crystal facet of RuSe2 is the dominant HER active site as it exhibited the lowest ΔGH* value. The in situ Raman spectra unravel the evolution process of the local electronic environment of Co-Se and Ru-Se bonds, which synergistically promotes the formation of CoOOH as the active intermediate during the OER. The superior catalytic efficiency and remarkable durability of RuSe2CoSe2/NC as an electrode for water splitting and zinc-air battery devices demonstrate its great potential for energy storage and conversion devices.

Facet‐Junction Induced Strong Metal Support Interaction for Enhanced Alkaline Hydrogen Evolution Reaction

AbstractStrong metal‐support interaction (SMSI) plays a critical role in enhancing the catalytic performance of electrocatalysts. Currently, effective approaches to enhance the SMSI effect in supported electrocatalysts still need to be developed, and a comprehensive atomic‐level understanding of the underlying reaction mechanisms remains unclear. In this study, a novel facet‐junction strategy is proposed to enhance the SMSI between the loaded Ru atoms and the Co3O4 support. By modulating the ratio of exposed facet for (111)/(100) crystal plane in Co3O4, the hydrogen evolution reaction (HER) performance can be dramatically enhanced by 560% and can achieve a Pt‐like HER activity with the overpotential of 45 mV. Detailed analysis with atomic‐resolution integrated differential phase contrast (iDPC)‐scanning transmission electron microscopy (STEM), atomic‐resolution high angle annular dark field (HADDF)‐STEM, and electron energy loss spectroscopy (EELS) further proved that with proper (111)/(100) crystal plane ratio, the intensified charge distribution near the facet‐junction region would modify the electronic structure around the active sites. This work provides new insights to enhance the SMSI and will contribute to the rational design of highly efficient electrocatalysts for water splitting.

A Quick Joule‐Heating Coupled with Solid‐Phase Synthesis for Carbon‐Supported Pd–Se Nanoparticles Toward High‐Efficiency Electrocatalysis

AbstractWith respect to the potential of palladium (Pd)‐based nanomaterials in catalyzing typical electrochemical reactions, herein, a strategy that couples the quick Joule‐heating with a solid phase synthesis for producing carbon‐supported Pd–Se nanoparticles with welcome features is reported, e.g., fine sizes, clean surfaces, and controlled crystal phases toward electrocatalysis of oxygen reduction reaction (ORR) and ethanol oxidation reaction (EOR) in an alkaline medium. Principally, the introduction of Se into Pd alters its electronic properties and weakens the adsorption of key reaction intermediates on the Pd–Se nanoparticles during the ORR and EOR process, thus endowing them with better electrocatalysis for the same electrochemical reactions. Impressively, the carbon‐supported Pd–Se nanoparticles exhibit phase‐dependent electrocatalysis toward ORR and EOR. In particular, the cubic Pd17Se15 nanoparticles supported on carbon substrate show mass activity of 0.206 A mgPd−1 and specific activity of 0.546 mA cm−2 at 0.9 V for ORR in 0.1 m KOH electrolyte, while the orthorhombic PdSe2 nanoparticles show a mass activity of 3.79 A mgPd−1 for EOR, higher than that of their cubic counterpart and commercial Pd/C catalyst. The universality of this synthetic strategy in manufacturing carbon‐supported noble metal chalcogenide nanoparticles and highlighting its potential in designing highly efficient electrocatalysts are emphasized.

Engineering low-valent molybdenum sites in CoMoO4 nanosheets to boost electrochemical nitrogen-rich wastewater treatment

Electrochemical coupling nitrate-to-ammonia (NO3–-to-NH3) with urea oxidation reaction (UOR) is attractive for both energy-saving ammonia synthesis and comprehensive nitrogen-rich wastewater treatment. However, developing the efficient electrocatalyst that simultaneously promotes hydrogenation of NO3– and UOR is still challenging. Here, we engineered the porous CoMoO4 nanosheets with rich low-valent Mo sites (Mo(L)-CoMoO4-x) as a difunctional electrocatalyst for both NO3–-to-NH3 and UOR. The Mo(L)-CoMoO4-x displayed high Faradaic efficiency (93.33%) and selectivity (91.16%) for NO3–-to-NH3 and low potential (1.31 V vs. RHE) at 100 mA cm−2 toward UOR. Impressively, a low cell voltage of 1.83 V was needed for coupling UOR with NO3–-to-NH3 in two-electrode system. Mechanism study revealed that the introduction of low-valent Mo sites in CoMoO4 nanosheets accelerated the activation kinetics and multistep hydrogenation of NO3–, and also promoted the reconstruction of active CoOOH species for UOR, resulting the difunctional catalytic property for NO3–-to-NH3 and UOR.