Ni–Fe nanocubes embedded with Pt nanoparticles for hydrogen and oxygen evolution reactions

Electrochemical water-splitting is widely regarded as one of the essential strategies to produce hydrogen energy, while Metal-organic frameworks (MOFs) materials are used to prepare electrochemical catalysts because of its controllable morphology and low cost. Herein, a series of trimetallic porous Pt-inlaid Ni–Fe nanocubes (NCs) are developed with bifunctions of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). In the process of prepare the electrochemical catalysts, Pt nanoparticles are uniformly embedded in the Fe–Ni PBA cube structure, and ascorbic acid is employed as a reducing agent to reduce Pt²⁺ to Pt nanoparticles. In this work, the cubic structure of Fe–Ni PBA is maintained and the noble metal Pt nanoparticles are embedded. Remarkably, the formation of PBA cubes, Pt inlay and reduction are completed in one step, and Pt nanoparticles are embedded by a simple method for the first time. By employing acid etching method, a porous structure is formed on the PBA cube, which increases the exposed area of the catalyst and provides more active sites for HER and OER. Due to the porous structure, highly electrochemical active surface area and the embedded of highly dispersed Pt nanoparticles, the porous 0.6 Ni–Fe–Pt nanocubes (NCs) exhibits excellently electrocatalytic performance and durable stability to HER and OER. In this work, for HER and OER, the Tafel slopes are 81 and 65 mV dec⁻¹, the overpotential η at the current density of 10 mA cm⁻² are 463 and 333 mV, and the onset potential are 0.444 and 1.548 V, respectively. And after a 12-h i-t test and 1000 cycles of cyclic voltammetry (CV), it maintained high stability and durability. This work opens up a new preparation method for noble metal embedded MOF materials and provided a new idea for the preparation of carbon nanocomposites based on MOF.     

Kinetics of hydrogen evolution reaction on stabilized Ni,Pt and Ni–Pt nanoparticles obtained by an organometallic approach

Both (Ni, Pt) and bimetallic (Ni_xPt; x = 1, 2, 3) nanoparticles have been synthesized by hydrogenation of Ni(cod)₂ ad Pt₂(dba)₃ in the presence of a weak coordinating ligand, hexadecylamine (CH₃(CH₂)₁₅NH_2, HDA). These nanostructures were characterized by different techniques (Fourier Transform-Infrared Spectroscopy (FT-IR), High-Resolution Transmission Electron Microscopy (HRTEM)), and were evaluated as Hydrogen Evolution Reaction electrocatalysts in 0.5 M sulfuric acid. The effects of varying the platinum amount during the synthesis were systematically studied by Cyclic Voltammetry (CV), polarization measurements and electrochemical impedance spectroscopy (EIS) techniques. HRTEM shows that the bimetallic nanostructures display a different morphology compared to that observed for pure Ni and Pt ones. The process of hydrogen adsorption–desorption in the as-prepared electrodes seems to occur in (110) and (100) facets. It was found that the increase in the activity for the HER is due to an increased electrochemical active surface area (ECSA) and/or stabilization in the case of elemental electrode materials; and to the effect of Pt amount in the case of the Ni–Pt nanostructures (synergistic effect leads to lower overpotential). It has been established that the main pathway for the HER is Volmer–Heyrovsky.     

Flower-like MOF-derived Co–N-doped carbon composite with remarkable activity and durability for electrochemical hydrogen evolution reaction

Electrochemical hydrogen evolution reaction (HER) is one of the most economical, sustainable, and attractive methods to produce hydrogen. Contemporarily, it is still a challenge to develop low-cost catalysts with high activity and durability for HER. Herein, we report a simple strategy to develop a Co–N-doped carbon electrocatalyst derived from a new cobalt metal-organic framework (MOF). The new flower-like 2D→3D MOF {[Co(BIPA)(5-OH-bdc)](DMF)}_n (1) was constructed based on bis(4-(1H-imidazol-1-yl)phenyl)amine (BIPA) and 5-hydroxyisophthalic acid (5-OH-H₂bdc). After that, the Co–N-doped carbon composite Co-MOF-800 was prepared via calcination of MOF 1. Interestingly, Co-MOF-800 exhibited excellent electrocatalytic activity and durability for HER. The onset potential (0.12 V) and E_j=10 value (0.193 V) of the Co-MOF-800 electrode were comparable to that of the most active non-precious metal HER electrocatalysts derived from other MOFs. The HER performance of Co-MOF-800 was stable without degradation even after long-term cycling.     

Morphological influence of graphitic carbon nanofibers by N–F dual-doping on Pt electrocatalytic activity and stability for oxygen reduction reaction in polymer electrolyte membrane fuel cells

Morphology of carbon nanofibers significantly effects Pt nanoparticles dispersion and specific interaction with the support, which is an important aspect in the fuel cell performance of the electrocatalysts. This study emphasizes, the defects creation and structural evolution comprised due to N–F co-doping on graphitic carbon nanofibers (GNFs) of different morphologies, viz. GNF-linearly aligned platelets (L), antlers (A), herringbone (H), and their specific interaction with Pt nanoparticle in enhancing the oxygen reduction reaction (ORR). GNFs–NF–Pt catalysts exhibit better ORR electrocatalytic activity, superior durability that is solely ascribed to the morphological evolution and the doped N–F heteroatoms, prompting the charge density variations in the resultant carbon fiber matrices. Amongst, H–NF–Pt catalyst performed outstanding ORR activity with exceptional electrochemical stability, which shows only 20 mV loss in the half-wave potential whilst 100 mV loss for Pt/C catalyst on 20,000 potential cycling. The PEMFC comprising H–NF–Pt as cathode catalyst with minimum loading of 0.10 mg cm^?2, delivers power density of 0.942 W cm^?2 at current density of 2.50 A cm^?2 without backpressures in H₂–O₂ feeds. The H–NF–Pt catalyst owing to its hierarchical architectures, performs well in PEMFC at the minimized catalyst loading with outstanding stability that can significantly decrease total price for the fuel cell.     

Effect of carbon content on Ni–Fe–C electrodes for hydrogen evolution reaction in seawater

Hydrogen evolution reaction (HER) on the Ni–Fe–C electrodes electrodeposited at current density ranging from 100 to 300 A/m², as well as their electrochemical properties in 3.5% NaCl solution at 90 °C and pH = 12, had been investigated by polarization measurements, EIS technique. It was shown that the carbon content and grain size of Ni–Fe–C coatings are affected by current density. In addition, the hydrogen evolution overpotential of Ni–Fe–C electrodes was related with carbon content and grain size. The Ni–Fe–C electrodes with optimum catalytic activity for the HER were found to contain the maximum carbon content 1.59% and the minimum grain size 3.4 nm. The results of a comparative analysis between carbon content and intrinsic activity are that carbon content plays an important role in intrinsic activity of Ni–Fe–C electrodes.     

In situ activation with Mo of Ni–Co alloys for hydrogen evolution reaction

In this study Ni–Co alloys have been activated during hydrogen electrochemical production by adding Mo ions into the alkaline electrolyte. After dissolving different amounts of sodium molybdate in the Na(OH) electrolyte, Ni–Co alloys were used as cathodes for hydrogen evolution reaction. Afterwards a comparison between hydrogen overvoltage measured on Ni–Co alloys with and without in situ activation has been made. The in situ activation clearly shows an improvement of electrocatalytic properties of Ni–Co alloys for hydrogen evolution reaction. Depending on the alloy the best conditions are reached with different amounts of sodium molybdate in the electrolyte. The values of exchange current density for Ni–Co alloys without Mo, are an average of about 4.1 10⁻⁶ A/cm², while by using in situ activation, these values are about 3.5·10⁻⁴ A/cm². Therefore, exchange current density presents a value nearly one hundred-fold higher when molybdate ions are present in solution. Moreover, two Tafel slope values have been determined for HER on Ni–Co alloys with and without Mo in situ activation. Those Tafel slope values are different, so as their range of both overvoltage and current density, probably highlighting a different kinetic mechanism.     

Electroless deposition of Ni–Cu–P on a self-supporting graphene with enhanced hydrogen evolution reaction activity

With the increasing issues of the energy crisis and environmental pollution, the development of clean energy has become an urgent task. Herein, self-supporting graphene (SSG) that could serve as the three-dimensional catalyst support is developed by electrochemically intercalating the flexible graphite paper (FGP) in 1 M KOH. Then, the Ni-base alloy is deposited on the SSG by electroless plating. The resulting electrode (Ni–Cu–P/SSG) exhibits excellent hydrogen evolution reaction (HER) electrocatalytic performance in 1 M KOH. The Ni–Cu–P/SSG catalyst just requires the overpotentials of 75 and 219 mV to reach 10 and 100 mA cm⁻², respectively. Besides, the Ni–Cu–P/SSG still maintains superior HER catalytic activity after the stability test of 12 h. The Ni–Cu–P/SSG composite catalyst with high catalytic activity, remarkable stability and facile preparation method has a significant influence on the extension of renewable energy preparation and application.     

Boosting hydrogen evolution activity and durability of Pd–Ni–P nanocatalyst via crystalline degree and surface chemical state modulations

Developing efficient, durable, and economical electro-catalysts for large-scale commercialization of hydrogen evolution (HER) is still challenging. Herein, we report for the first time, to the best of our knowledge, a Pd-based ternary metal phosphide as an active and stable HER catalyst. The face-centered-cubic Pd–Ni–P nanoparticles (NPs) annealed at 400 °C show the best HER activity with a low overpotential of 32 mV to realize a current density of 10 mA cm⁻² and a high mass activity of 1.23 mA μg⁻¹_Pd, superior to Pd NPs, Pd–P NPs, Pd–Ni NPs, and Pd–Ni–P NPs annealed under different temperatures. Moreover, this catalyst is also highly stable during 20 h of continuous electrolysis. Notably, the easily fabricated Pd–Ni–P NPs are among the most active Pd-based HER catalysts. This work indicates that Pd-based metal phosphides could be potentially applied as a type of practical HER catalyst and might inform the fabrication of analogous materials for hydrogen-related applications.     

Synthesis and characterisation of platinum–cobalt–manganese ternary alloy catalysts supported on carbon nanofibers: An alternative catalyst for hydrogen evolution reaction

A systematic method for obtaining a novel electrode structure based on PtCoMn ternary alloy catalyst supported on graphitic carbon nanofibers (CNF) for hydrogen evolution reaction (HER) in acidic media is proposed. Ternary alloy nanoparticles (Co0.6Mn0.4 Pt), with a mean crystallite diameter under 10 nm, were electrodeposited onto a graphitic support material using a two-step pulsed deposition technique. Initially, a surface functionalisation of the carbon nanofibers is performed with the aid of oxygen plasma. Subsequently, a short galvanostatic pulse electrodeposition technique is applied. It has been demonstrated that, if pulsing current is employed, compositionally controlled PtCoMn catalysts can be achieved. Variations of metal concentration ratios in the electrolyte and main deposition parameters, such as current density and pulse shape, led to electrodes with relevant catalytic activity towards HER. The samples were further characterised using several physico-chemical methods to reveal their morphology, structure, chemical and electrochemical properties. X-ray diffraction confirms the PtCoMn alloy formation on the graphitic support and energy dispersive X-ray spectroscopy highlights the presence of the three metallic components from the alloy structure. The preliminary tests regarding the electrocatalytic activity of the developed electrodes display promising results compared to commercial Pt/C catalysts. The PtCoMn/CNF electrode exhibits a decrease in hydrogen evolution overpotential of about 250 mV at 40 mA cm⁻² in acidic solution (0.5 M H₂SO₄) when compared to similar platinum based electrodes (Pt/CNF) and a Tafel slope of around 120 mV dec⁻¹, indicating that HER takes place under the Volmer-Heyrovsky mechanism.     

Silicotungstic acid stabilized Pt–Ru nanoparticles supported on carbon nanofibers electrodes for methanol oxidation

Silicotungstic acid stabilized Pt–Ru nanoparticles supported on Functionalized Carbon Nanofibers have been prepared by a microwave-assisted polyol process. The samples were characterized by XRD, SEM and TEM analysis. The electro-catalytic activities of the prepared composites (20% Pt–Ru/STA–CNF) were examined by using Cyclic Voltammetry (CV) for oxidation of methanol. The electro-catalytic activity of the carbon nanofiber based composite (20% Pt–Ru/STA–CNF) electrode for methanol oxidation showed better performance than that of commercially available Johnson Mathey 20% Pt–Ru/C and 20% Pt–Ru/STA–C catalyst. The results imply that carbon nanofiber based STA composite electrodes are excellent potential candidates for application in direct methanol fuel cells.     

Bimetallic palladium–iridium alloy nanoparticles as highly efficient and stable catalyst for the hydrogen evolution reaction

Addressed herein, a highly efficient, durable and uniformly dispersed activated carbon supported palladium–iridium nanomaterials (3.42 ± 0.34 nm) were reported for the first time as a catalyst in dimethylamine-borane dehydrogenation reaction at the room temperature. The activated carbon supported palladium-iridium nanosheet (Pd–Ir NPs) is obtained by a simple ultrasonic reduction method, and the fabricated nanocatalyst have been defined by Ultra-Violet-Visible (UV–VIS), Raman spectroscopy, X-Ray Diffraction (XRD), X-Ray Photoelectron Spectroscopy (XPS), Transmission Electron Microscopy (TEM) and High-Resolution Transmission Electron Microscopy (HR-TEM). These newly prepared Pd–Ir nanocomposites were found to be highly efficient and stable for dehydrocoupling of dimethylamine borane. The catalytic activity of the Pd–Ir NPs was excellent by showing the one of the best catalytic activity with a very high turnover frequency (295.1 h^?1) and low E_a value of 36.6 ± 2 kJ/mol for DMAB dehydrocoupling. Another important fact about the prepared catalyst is the reusability of the catalyst was very high and easily reused five times without any significant decrease in their catalytic performance. In the current work, the synthesize, characterization and the catalytic performance of the Pd–Ir nanoparticles for the dehydrogenation of the DMAB reaction will be discussed in detail.     

Electrochemical fabrication of Ni–Mo nanostars with Pt-like catalytic activity for both electrochemical hydrogen and oxygen evolution reactions

Synthesis of electrocatalysts with excellent performance for hydrogen and oxygen evolution are the main challenges for production of hydrogen by electrochemical water splitting method. Here, Ni–Mo nanostars were created by electrochemical deposition process at different morphologies and their electrocatalytic behavior was studied for hydrogen and oxygen evolution reactions in 1.0 M KOH solution. Increased electrochemically active surface area due to the nanostars formation, improved intrinsic electrocatalytic activity, increased surface wettability, as well as being binder-free during electrode production, resulted in excellent electrocatalytic behavior. For optimized condition, 60 mV and 225 mV overpotential are needed for generating the current density of 10 mA.cm-² in HER and OER process respectively in the alkaline medium. The lower slope of the electrode compared to the other electrodes also indicated that the kinetics of HER on the surface of the electrode was better. Also, there was very little change in the potential during the stability test, indicating the excellent electrocatalytic stability of the synthesized electrode. The present study introduces a rational, cost-effective and binder-free method for the synthesis of high performance electrocatalysts.     

Nanostructured Ni–Co alloy electrodes for both hydrogen and oxygen evolution reaction in alkaline electrolyzer

Ni–Co alloy nanostructured electrodes with high surface area were investigated both as a cathode and anode for an alkaline electrolyzer. Electrodes were obtained by template electrosynthesis at room temperature. The electrolyte composition was tuned in order to obtain different NiCo alloys. The chemical and morphological features of nanostructured electrodes were evaluated by EDS, XRD and SEM analyses. Results show that electrodes with different composition of Ni and Co, made of nanowires well anchored to the substrate, were obtained. For both hydrogen and oxygen evolution reactions, electrochemical and electrocatalytic tests, performed in 30% w/w KOH aqueous solution, were carried out to establishing the best alloy composition. Mid-term tests conducted at a constant current density were also reported. Nanostructured electrodes with a Co atomic composition of 94.73% have the best performances for both hydrogen and oxygen evolution reactions. In particular, with this alloy, a potential of ?0.43 V (RHE) and of 1.615 V (RHE) was measured for hydrogen and oxygen evolution reaction at ?50 mA cm^?2 and at 50 mA cm^?2, respectively, after 6 h of electrolysis. The calculated Tafel's slopes for HER and OER were ?0.105 and 0.088 V/dec, respectively. Furthermore, HER and OER η₁₀ potential values were measured founding ?0.231 V (RHE) and 1.494 V (RHE) respectively.     

Pt and Pt–Ag nanoparticles supported on carbon nanotubes (CNT) for oxygen reduction reaction in alkaline medium

In this work, we investigated the effect of the carbon nanotubes (CNT) as alternative support of cathodes for oxygen reduction reaction (ORR) in alkaline medium. The Pt and Pt–Ag nanomaterials supported on CNT were synthesized by sonochemical method. The crystalline structure, morphology, particle size, dispersion, specific surface area, and composition were investigated by XRD, SEM-EDS, TEM, HR-TEM, N₂ adsorption-desorption and XPS characterization. The electrochemical activity for ORR was evaluated by cyclic voltammetry (CV), linear sweep voltammetry (LSV), and electrochemical impedance spectroscopy (EIS) in alkaline medium. The electrochemical stability was researched by an accelerated degradation test (ADT). Pt/CNT showed the better electrocatalytic activity towards ORR compared with Pt–Ag/CNT and Pt/C. Pt/CNT exhibited higher specific activity (1.12 mA cm^?2 _Pt) than Pt/C (0.25 mA cm^?2 _Pt) which can be attributed to smaller particle size, Pt-CNT interaction, and Pt load (5 wt%). The Pt monometallic samples supported on CNT and Vulcan showed higher electrochemical stability after ADT than Pt–Ag bimetallic. The ORR activity of all materials synthesized proceeded through a four-electron pathway. Furthermore, the EIS results showed that Pt/CNT exhibited the lower resistance to the transfer electron compared with conventional Pt/C and Pt–Ag/CNT.     

Electrochemical activity and stability of dealloyed Pt–Cu and Pt–Cu–Co electrocatalysts for the oxygen reduction reaction (ORR)

A comparative study of the electrochemical stability of Pt₂₅Cu₇₅ and Pt₂₀Cu₂₀Co₆₀ alloy nanoparticle electrocatalysts in liquid electrolyte half-cell environment was conducted. The aforementioned catalysts were shown to possess improved resistance to electrochemical surface area (ECSA) loss during voltage cycling relative to commercially available pure Pt electrocatalysts. The difference in ECSA loss was attributed to their initial mean particle size, which varied depending on the temperature at which the alloy catalysts were prepared (e.g. 600, 800 and 950 °C). Higher preparation temperatures resulted in larger particles and lead to lower ECSA loss. Liquid electrolyte environment short-term durability testing (5000 voltages cycles) revealed the addition of cobalt to be beneficial as ternary compositions exhibited stability advantages over binary catalysts.     

A low-cost platinum-free electrocatalyst based on carbon quantum dots decorated Ni–Cu hierarchical nanocomposites for hydrogen evolution reaction

The effective Ni–Cu bimetallic nanocomposite was deposited on a glassy carbon electrode, GCE, that modified with carbon quantum dots, CQDs. The deposition process was done by one-step and controllable electrochemical method in an electrolyte of nickel and copper sulfate. The structural properties of composite studied by techniques such as X-ray diffraction, XRD, energy dispersive X-ray analysis, EDX, field emission scanning electron microscopy, FESEM, and transmission electron microscopy, TEM. Ni–Cu/RCQDs nanocomposite was applied as a cathode for catalysis of hydrogen evolution reaction, HER, in acidic media by cyclic voltammetry, CV, linear sweep voltammetry, LSV, chronoamperometry, CA, and electrochemical impedance spectroscopy, EIS. The onset potential, E_onset, for the evolution of hydrogen at the current density of −10 mA cm⁻² for Ni–Cu/RCQDs was −230 mV vs. SHE that had a 100 mV shift to positive voltages in comparison with Ni–Cu catalyst. It can be related to the synergistic effect between metallic nanoparticles. V. dec⁻¹, respectively.     

Potentiostatic electrodeposition of cost-effective and efficient Ni–Fe electrocatalysts on Ni foam for the alkaline hydrogen evolution reaction

The hydrogen evolution reaction (HER) using earth-abundant noble-metal-free catalysts has gained substantial interest in electrocatalytic water splitting technologies, particularly in water-alkali electrolyzers. The development of highly-efficiency and durable inexpensive electrocatalysts to accelerate the kinetics of HER is still a formidable challenge. In this study, nickel–iron (Ni–Fe) electrocatalyst directly grown on backbones of Ni foam (NF) substrate was facile prepared via one-step potentiostatic electrodeposition method. The obtained Ni–Fe electrocatalyst exhibits a film-like structure. Owing to high electrical conductivity and composition optimization, the synthesized Ni–Fe electrocatalyst with Ni/Fe atomic ratio of c.a. 65:35 possesses an attractive electrocatalytic activity with low overpotentials of 142, 205, and 239 mV at 10, 50, and 100 mA·cm^?2 in alkaline electrolyte, respectively.     

One-step potentiostatic electrodeposition of Ni–Se–Mo film on Ni foam for alkaline hydrogen evolution reaction

Exploring efficient, abundant, low-cost and stable materials for hydrogen evolution reaction (HER) is highly desired but still a challenging task. Herein, Ni–Se–Mo electrocatalysts supported on nickel foam (NF) substrate were synthesized by a facile one-step electrodeposition method. The Ni–Se–Mo film presents high electrocatalytic activity and stability toward HER, with a low overpotential of 101 mV to afford a current density of 10 mA cm⁻² in 1.0 M KOH medium. Such excellent HER performance of Ni–Se–Mo film induced by the synergistic effects from Mo-doped Ni–Se film leads to the fast electron transfer. This work provides the validity of interface engineering strategy in preparing highly efficient transition metal chalcogenides based HER electrocatalysts.     

Tuning of electrocatalytic activity of Mn–O–Co composite for alkaline hydrogen evolution reaction

We report the enhancement in electrocatalytic activity of Mn–O–Co composite electrode developed through chemical reduction method. The Mn–O–Co composite electrode exhibits high catalytic activity with a low Tafel slope of 123 mV dec⁻¹ and a low overpotential of 117 mV at a current density of 10 mA cm⁻². The enhancement in electrocatalytic activity of Mn–O–Co composite electrode is due to the synergistic activity of MnO and CoO with the NiP matrix. The intermetallic interaction among the half-filled orbitals of manganese with the fully occupied orbitals of cobalt and nickel leads to an effective electron delocalization in the catalytic system which enhances the HER performance of the coating. The C_dl value of the composite electrode is in the order of 254 μF, which is approximately ten fold higher than the bare NiP coating, due to the enhancement in interaction between the Mn–O–Co composite electrode and the reactive species in the HER medium. The Mn–O–Co composite electrode shows promising characteristics as an electrocatalyst with long term stability and remarkable competency with the commercially available electrodes.     

Synthesis and characterization of macroporous Ni,Co and Ni–Co electrocatalytic deposits for hydrogen evolution reaction in alkaline media

In this work, macroporous Ni, Co and Ni–Co electrodes have been developed by co-deposition at high current density on stainless steel (AISI 304) substrates. The obtained materials were characterized both morphologically and chemically by confocal laser scanning microscopy, and SEM coupled with EDX analysis. The activity for hydrogen evolution reaction (HER) on the obtained layers was assessed by using pseudo-steady-state polarization curves and electrochemical impedance spectroscopy (EIS) in alkaline solution (30 wt.% KOH). The electrochemical results show that HER on these electrodes takes place by the Volmer–Heyrovsky mechanism. The synthesized coatings present higher catalytic activity for HER than commercial smooth Ni electrode. As the Co content increases in the electrodeposition bath the obtained structures show lower surface roughness factors. Ni–Co deposit with a Co content of 43 at.% manifests the highest intrinsic activity for HER as a consequence of the synergetic combination of Ni and Co.