Facile in-situ deposition of three-dimensional Pt nanoballs of nickel nanorods heterojunction electrodes for hydrogen evolution reaction

Hydrogen is a kind of renewable energy for a friendly environment and can promote carbon emission reduction. The Platinum catalytic electrode is widely applied in hydrogen evolution reaction (HER) of water due to its low overpotential. However, it has affected its commercial application because of its high cost. Therefore, developing heterojunction catalysts with Platinum for HER is an effective way to achieve large-scale hydrogen production. In this work, we present a novel PtNBs/NiNRs heterojunction catalyst via the Pt nanoballs in-situ deposition on Ni nanorods array. The results demonstrate that the PtNBs/NiNRs electrodes have superior catalytic activity for HER in an alkaline condition. The hydrogen overpotential of PtNBs/NiNRs is −61.6 mV (RHE) in the alkaline solution, which is lower than the Pt electrode of −184mV. The Tafel plots and EIS were employed to investigate the mechanism and kinetics of the PtNBs/NiNRs in the alkaline solution. The nanostructures of Ni nanorobs and the Pt nanoballs active sites decrease the charge transfer resistance and increase the charge capacitance for the HER process compared to the Pt electrode. The PtNBs/NiNRs heterojunction catalyst electrodes demonstrate promising applications in HER because of their facile preparation, high efficiency, and low value.     

Pt/Fe-NF electrode with high double-layer capacitance for efficient hydrogen evolution reaction in alkaline media

The electrode with high catalytic activity, low hydrogen overpotential and low cost is desired for hydrogen evolution reaction (HER) via electrocatalytic water splitting. In this study, Pt/Fe-Ni foam (Pt/Fe-NF) electrode was synthesized via cathodic electrodeposition followed by impregnation deposition. Physical and electrochemical properties of Pt/Fe-NF, NF and Pt/NF electrodes were characterized by various techniques. The Pt/Fe-NF electrode exhibited better electrochemical activity for HER under alkaline condition than those of Pt/NF and NF electrodes, owing to the introduction of zero valences Pt and Fe onto the NF, and synergetic effect resulted from the formation of Fe-Ni alloy. Furthermore, Pt/Fe-NF electrode showed extremely high double-layer capacitance (69.1 mFcm^?2), suggesting high active sites for the Pt/Fe-NF. Tafel slope of Pt/Fe-NF was 59.9 mV dec^?1, indicating that the Volmer-Heyrovsky HER mechanism was the rate-limiting step. The Pt/Fe-NF electrode with great electrocatalytic activity is a promising electro-catalyst for industrial hydrogen production from alkaline electrolyte.     

Enhancement of hydrogen evolution reaction by Pt nanopillar-array electrode in alkaline media and the effect of nanopillar length on the electrode efficiency

Pt nanopillar-array 3D electrodes with nanopillar length of 150, 450 and 900 nm and nanopillar density of ~10⁹ cm⁻² were fabricated. Their catalytic activity for hydrogen evolution reaction (HER) was evaluated by linear sweep voltammetry and electrochemical impedance spectroscopy. In comparison with straightly electrodeposited black Pt film and forged Pt sheet electrodes, the HER current density has been significantly improved by the nanopillar-array architecture. The overpotential of HER at current density of 10 mA cm-2 at 26 °C is as low as 78 mV, lower than the black Pt film of 107 mV and the Pt sheet of 174 mV. The improvement of HER is ascribed to the low charge transfer resistance of the 3D electrode and the high desorption capability of hydrogen bubbles at the nanotips. Interestingly, the nanopillar-array 3D electrode has an optimal nanopillar length for HER. The mechanisms for the optimal nanopillar length were investigated here.     

Electrocatalysis of hydrogen evolution reaction on tri-metallic Rh@Pd/Pt(poly) electrode

Hydrogen evolution reaction (HER) was investigated in alkaline solution on tri-metallic Rh@Pd/Pt(poly) electrode, prepared by spontaneous deposition of Rh on top of Pd/Pt(poly) electrode with intermediate Pd coverage of 35%. Characterization of tri-metallic catalyst was performed by electrochemical methods of cyclic voltammetry and CO stripping voltammetry, while its activity for HER was tested by linear sweep voltammetry in 0.1 M NaOH. Rh@Pd/Pt(poly) catalyst has shown superior catalytic activity for HER with respect to initial Pt(poly) and both corresponding bimetallic Pd/Pt(poly) and Rh/Pt(poly) electrodes. This was explained by a strong synergistic electronic interaction between three metals in close contact induced at a number of different active sites across the surface of tri-metallic catalyst, which results with lowering of the binding energy for the adsorption of H intermediate species.     

Molybdenum/graphene – Based catalyst for hydrogen evolution reaction synthesized by a rapid photothermal method

Catalysis of the hydrogen evolution reaction (HER) is important in the development of an energy economy based on clean hydrogen gas. In this work, we report a new catalyst material for the generation of hydrogen via hydronium reduction. The new material, which consists of MoO₂, sulfur, and graphene, was prepared by co-reduction of molybdenum salt and graphite oxide in air in the presence of focused solar radiation. The potential utility of this material for HER catalysis was evaluated by cyclic and linear-sweep voltammograms and compared against a Pt/C commercial catalyst. The MoO₂/graphene hybrid nanocomposite exhibits a Tafel slope of 47 mV/dec and hydrogen evolution at a potential only ∼120 mV more negative than the standard Pt/Carbon catalyst at 10 mA/cm² current density. The hydrogen gas generated by the catalytic material was measured using gas chromatography. The simple synthesis and low overpotential suggests that this hybrid composite has potential as an HER catalyst.     

Simple cathodic deposition of FeS/NiS-activated Ni/NiO heterojunctions for high-concentration overall water splitting reactions

To produce hydrogen through electrolysis of water, the creation of effective and affordable electrodes for overall water splitting is essential. We present the deposition of active oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) components on the same NF in this work, enabling the synergistic effect of FeS/NiS and Ni/NiO active components for effective overall water splitting. In alkaline electrolytes, NiFe@NF electrodes deposited using a straightforward two-step cathodic deposition process at various currents exhibit good catalytic activity for both OERs and HERs. For the electrode to be stable over time, Ni/NiO is firmly bonded to NF, and the specific surface areas of the FeS/NiS nanoflowers provide efficient electron transport. The electrode outperformed the RuO₂ electrode by achieving a current density of 10 mA cm⁻² at an OER overpotential of 168 mV. Additionally, the HER only needs a 84 mV overpotential to reach a current density of 10 mA cm⁻². In addition, an electrolytic cell constructed with the same NiFe@NF as the cathode and anode requires a cell voltage of only 1.47 V to achieve a current density of 10 mA cm⁻². It can operate stably for a long time (120 h) at high temperature and high concentration conditions. This work highlights the importance of active components with simultaneous OER and HER activities on electrodes for efficient catalytic applications in overall water splitting.     

Interface engineering of crystalline/amorphous Pt/TeOx nanocapsules for efficient alkaline hydrogen evolution

Hydrogen evolution reaction (HER) is an important process in electrochemical energy technology, and efficient electrocatalysts are of great significance for renewable and sustainable energy conversion. Here, we report a facile hydrothermal and heat treatment process to synthesize a series of Pt-based nanocapsules (NCs) as an effective hydrogen evolution catalyst. The Pt/TeO_x NCs exhibit excellent HER activity in an alkaline medium. The Pt/TeO_x NCs only need the overpotential of 33 mV to achieve the current density of 10 mA cm⁻², and the Tafel slope was as low as 29 mV dec⁻¹, which was even better than that of commercial Pt/C. Detailed experimental characterizations demonstrate that the interface between the crystalline Pt/amorphous TeO_x and the strong electron transfer contribute to alkaline HER activity. This work opens up a new direction for the preparation of efficient catalysts for electrocatalytic reactions or other conversion filed.     

Electrodeposited Ni-Co-Sn alloy as a highly efficient electrocatalyst for water splitting

Water splitting to produce hydrogen and oxygen is considered as a feasible solution to solve the current energy crisis. It is highly desirable to develop inexpensive and efficient electrocatalyst for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). In this paper, nanostructured Ni-Co-Sn alloys were electrodeposited on copper foil and the excellent electrocatalytic performances for both HER and OER in alkaline media were achieved. The optimized Ni-Co-Sn electrode shows a low onset overpotential of −18 mV and a small Tafel slope of 63 mV/dec for the HER, comparable to many state-of-the-art non-precious metal HER catalysts. For the OER, it produces an overpotential of 270 mV (1.50 V vs. RHE) at current density of 10 mA/cm², which is better than that of the commercial Ir/C catalyst. In addition to high electrocatalytic activities, it exhibits good stability for both HER and OER. This is the first report that Ni-Co-Sn is served as a cost-effective and highly efficient bifunctional catalyst for water splitting and it will be of great practical value.     

Fabrication of platinum thin films for ultra-high electrocatalytic hydrogen evolution reaction

While the noble metals (e.g., platinum, (Pt)) remain the benchmark electrocatalyst for the hydrogen evolution reaction (HER), their mass production require a reduced metal loading and faster fabrication protocols. The aim of the present work is to prepare Pt thin films by simple and fast fabrication technique, and to evaluate their performance for HER. The thin films of Pt are grown on two substrates, namely titanium foil (Ti) and nickel foam (NF), using a single step aerosol assisted chemical vapor deposition (AACVD) method. The film deposition time are varied from 20 to 60 min. Microscopic analyses suggest a gradual evolution of the films into percolated and/or porous nanostructures, a feature that remains highly desired to allow the maximum access of active sites. The performance of the as-prepared electrodes is evaluated by monitoring the HER in acidic electrolyte. The Pt film on nickel foam (Pt/NF) exhibits better electrical conductivity and smaller charge transfer resistance, while the film deposited on the Ti foil (Pt/Ti) demonstrates superior catalytic activity per active sites. The as-prepared Pt/Ti and Pt/NF electrodes produce 10 mA cm⁻² at overpotential of 28 mV and 26 mV, respectively, better in performance than commercial Pt/C electrode (~39 mV), set a new bench mark electrocatalyst for the HER.     

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.     

Facile galvanic replacement method for porous Pd@Pt nanoparticles as an efficient HER electrocatalyst

In realm of renewable energy, development of an efficient and durable electrocatalyst for H₂ production through electrochemical hydrogen evolution reaction (HER) is indispensable. Herein, we demonstrate a simple preparation of carbon-supported nanoporous Pd with surface coated Pt (CS–PdPt) by a simple galvanic replacement reaction (GRR). The phase purity and porosity have been confirmed by XRD, HRTEM, and N₂ sorption techniques. As HER electrocatalyst, CS-PdPt showed a low overpotential of 26 mV in 0.5 M H₂SO₄ at current density of 10 mA cm⁻², which is lower than the commercial Pt/C electrode. The CS-PdPt catalyst exhibits an overpotential of 46 mV in 1 M KOH, and 50 mV in neutral buffer (1 M PBS) at 10 mA cm⁻². The CS-PdPt furnished with small Tafel values of 33, 88, and 107 mV dec⁻¹ in acidic, alkaline, and neutral medium, respectively. Accelerated durability test at 100 mV s⁻¹ for 1000 cycles demonstrated a negligible change in HER activity.     

Boosting hydrogen evolution on NiFeZn electrocatalyst by defect surface modulation using alkali etching

Developing highly efficient catalysts using facile approaches is important for accelerating the slow reaction kinetics of the alkaline hydrogen evolution reaction (HER) and ensuring cost-effective hydrogen production. In this study, we reported a facile alkali etching method to boost the HER activity immediately after electrodeposition of a NiFeZn catalyst on Ti paper. During etching, (oxy)hydroxides were formed on the surface, and Zn species were etched from the deposits, which resulted in a roughened surface with more valleys generated between grains, facilitating a faster mass transport during the electrochemical reaction. The etched catalyst exhibited a boosted HER overpotential of 57 mV at ?10 mA/cm² and accelerated HER kinetic with Tafel slope of 97 mV/dec compared with that of the pristine catalyst. Our results demonstrated an efficient approach for boosting the catalyst activity in the alkaline HER.     

NiCoP nanoarchitectures: One-step controlled electrodeposition and their application as efficient electrocatalysts for boosting hydrogen evolution reaction

Designing non-precious and long-lasting electrocatalysts with enhanced catalytic properties for hydrogen evolution reaction (HER) is a fundamental approach to address the needs for hydrogen industry and overcome the current challenges in sustainable energy generation. Herein, we present ternary NiCoP nanostructures synthesized through a direct and controlled electrochemical deposition at room temperature as highly efficient electrocatalysts for HER. Different Ni/Co ratios in the alloy were investigated resulting in different nanoarchitectured morphologies, chemical compositions and HER performances, in turn. The NiCoP–I alloy exhibited a nanoparticulated morphology comprising well-defined nanoparticles of ～20–30 nm which evolved to nanoparticulated caps at prolonged electrodeposition times presenting a large electrochemical surface area of 526 cm². The NiCoP–I electrocatalyst demonstrated a small Tafel slope of 49 mV dec^?1 and an ultra-low overpotential of 68 mV vs. RHE at ?10 mA cm^?2 in alkaline solution which well rivals to that of Pt foil and outmatches its binary alloy counterparts.     

The catalytic effect of trimetallic alloy modified C-felt electrodes on hydrogen evolution reaction

In this study, Ni, NiFe, and Pt are electrochemically deposited on the porous carbon felt for various periods to increase catalytic efficiency and hydrogen gas production, which is investigated in an alkaline medium. The prepared electrodes are characterized by using electrochemical impedance spectroscopy, linear sweep voltammetry, potentiodynamic polarization, cyclic voltammetry, scanning electron microscopy, and X-ray diffraction methods. In addition, hydrogen gas volume is measured by applying the electrolysis process to the electrodes prepared in 1.0 M KOH. It is observed that the most effective Ni deposition time on carbon felt is 20 min. Nickel deposited electrodes were coated with Ni&Fe and Pt in different periods to increase the catalytic effect of the electrode. The highest catalytic effect on the hydrogen evolution reaction was obtained from the C#Ni₂₀NiFe₁₀@Pt₄₅ electrode. Applied of a ?0.2 V_SHE overpotential, 80 mA cm^?2 current density is obtained. The mechanism is determined as Volmer-Heyrovsky and rate determined step is Volmer.     

Boosting activity and stability by coupling Pt–Ni nanoparticles with La-modified flexible carbon nanofibers for hydrogen evolution reaction

Platinum (Pt) is considered as the most efficient catalyst for hydrogen evolution reaction (HER) with a nearly zero overpotential, but it is limited by the high cost and poor stability. Herein, we report an efficient electrocatalyst of Pt–Ni alloy nanoparticles (NPs) supported on the La-modified flexible carbon nanocomposite fibers (PtNi@La-CNFs) for HER. The rare earth metal oxide in the catalyst has a structure-effect relationship with the carbon fibers to form a flexible fiber membrane. Experimental results show that the macroscopic and microscopic properties of carbon nanocomposite fibers can be optimized by doping La₂O₃, and the Pt–Ni NPs can be anchored effectively. The Pt₁Ni₁@La-CNFs electrocatalyst exhibits a small overpotential of 32 mV to achieve current density of 10 mA cm^?2 with a low Tafel slope of 51 mV dec^?1 in alkaline medium, outperforming that of Pt@La-CNFs and the commercial Pt/C catalyst. This study reveals that the multiple coupling effect of rare earth compound, precious metal, and transition metal in composite catalyst can tailor its the electronic configuration, and results in an enhanced HER performance. This work opens up a novel approach to design high active and low cost Pt-based HER catalysts.     

Physical insights into alkaline overall water splitting with NiO microflowers electrodes with ultra-low amount of Pt catalyst

Electrochemical water splitting represents a promising alternative to conventional carbon-based energy sources. The hydrogen evolution reaction (HER) is a key process, still if conducted in alkaline media, its kinetics is slow thus requiring high amount of Pt based catalysts. Extensive research has been focused on reducing Pt utilization by pursuing careful electrode investigation. Here, a low-cost chemical methodology is reported to obtain large amount of microflowers made of interconnected NiO nanowalls (20 nm thick) wisely decorated with ultralow amounts of Pt nanoparticles. These decorated microflowers, dispersed onto graphene paper by drop casting, build a high performance HER electrode exhibiting an overpotential of only 66 mV at current density of 10 mA cm^?2 under alkaline conditions. Intrinsic activity of catalyst was evaluated by measuring the Tafel plot (as low as 82 mV/dec) and turnover frequencies (2.07 s^?1 for a Pt loading of 11.2 μg cm^?2). The effect of Pt decoration has been modelled through energy band bending supported by electrochemical analyses. A full cell for alkaline electrochemical water splitting has been built, composed of Pt decorated NiO microflowers as cathode and bare NiO microflowers as anode, showing a low potential of 1.57 V to afford a current density of 10 mA cm^?2 and a good long-term stability. The reported results pave the way towards an extensive utilization of Ni based nanostructures with ultralow Pt content for efficient electrochemical water splitting.     

Efficient hydrogen evolution performance of phase-pure NiS electrocatalysts grown on fluorine-doped tin oxide-coated glass by facile chemical bath deposition

The production of hydrogen, the future fuel, on stable, efficient, and robust electrocatalysts represents an attractive approach for the conversion and storage of carbon-free energy resources. In this study, earth-abundant nickel sulfide (NiS) electrocatalyst were grown on fluorine-doped tin oxide (FTO) substrate by a simple and cost-effective chemical bath deposition for hydrogen evolution reaction (HER). Energy dispersive X-ray analysis and X-ray photoelectron spectra indicated the presence of highly pure NiS. The HER performance of the catalyst was examined in alkaline solution (1.0 M NaOH; pH = 13.5). Notably, NiS film prepared at 100 °C demonstrated superior HER activity with an overpotential of 290 mV to afford a current density of 10 mA/cm² and a Tafel slope of 143.4 mV/dec which are among the promising results obtained for sulfide-based HER electrocatalysts. The catalyst exhibited 100% faradaic efficiency and electrochemical stability which indicate its potential as noble-metal-free HER electrocatalyst.     

Preparation of Pt/C electrode with double catalyst layers by electrophoresis deposition method for PEMFC

Pt/C double catalyst layer (DCL) electrodes are prepared by pulsed electrophoresis deposition (PED) method from a Pt colloidal solution as a plating bath. The PED is optimized by varying the deposition time in a galvanostatic mode. The catalyst layers of the electrodes prepared by this method are structurally characterized by EDX and SEM studies. The catalytic activities of Pt/C DCL electrodes are evaluated by cyclic voltammetry technique. The loading amount of the Pt catalyst is controlled by varying the deposition time. With the same Pt catalyst loading, the DCL electrode has enhanced catalytic activity than single catalyst layer (SCL) electrode.     

Facile hydrothermal synthesis of rare earth phosphate for boosting hydrogen evolution reaction

The water electrolysis process has attracted great attention due to the production of high energy density pure hydrogen. However, the involved cell reactions in this process such as hydrogen and oxygen evolution reactions are kinetically sluggish and demands high input energy to accelerate the rate of these reactions. Therefore, the development and application of efficient electrocatalyst is essential for hydrogen evolution reaction (HER) as well as oxygen evolution reaction (OER). In the present work, we have successfully synthesized two rare earth phosphates through the hydrothermal route and used as a catalysts towards HER in an acidic medium. The rare earth phosphate PrPO₄ exhibits better catalytic activity than YPO₄ catalyst. The overpotential of PrPO₄, YPO₄ and standard Pt/C were found as 147, 484.3 and 58 mV vs. reversible hydrogen electrode, respectively, to reach current density 10 mA·cm^?2 and corresponding Tafel slopes were found as 107.58, 118.73 and 80.89 mV decade^?1, respectively in 0.5 M H₂SO₄. The catalytic activity of PrPO₄ (472.83 mA·cm^?2) overcome standard Pt/C (179.60 mA·cm^?2) at high overpotential 450 mV vs. reversible hydrogen electrode. The prepared PrPO₄ shows efficient electrocatalytic activity towards HER in acidic medium because it possess high BET surface area, large ECSA value and small charge transfer resistance than YPO₄.     

Three-dimensional ZnCo/MoS2–Co3S4/NF heterostructure supported on nickel foam as highly efficient catalyst for hydrogen evolution reaction

Exploring inexpensive and earth-abundant electrocatalysts for hydrogen evolution reactions is crucial in electrochemical sustainable chemistry field. In this work, a high-efficiency and inexpensive non-noble metal catalysts as alternatives to hydrogen evolution reaction (HER) was designed by one-step hydrothermal and two-step electrodeposition method. The as-prepared catalyst is composed of the synergistic MoS₂–Co₃S₄ layer decorated by ZnCo layered double hydroxides (ZnCo-LDH), which forms a multi-layer heterostructure (ZnCo/MoS₂–Co₃S₄/NF). The synthesized ZnCo/MoS₂–Co₃S₄/NF exhibits a small overpotential of 31 mV and a low Tafel plot of 53.13 mV dec^?1 at a current density of 10 mA cm^?2, which is close to the HER performance of the overpotential (26 mV) of Pt/C/NF. The synthesized ZnCo/MoS₂–Co₃S₄/NF also has good stability in alkaline solution. The excellent electrochemical performance of ZnCo/MoS₂–Co₃S₄/NF electrode originates from its abundant active sites and good electronic conductivity brought by the multilayer heterostructure. This work provides a simple and feasible way to design alkaline HER electrocatalysts by growing heterostructures on macroscopic substrates.