Electrocatalytic properties for the hydrogen evolution of the electrodeposited Ni–Mo/WC composites

The catalytical activity for the hydrogen evolution reaction (HER) of the electrodeposited Ni–Mo/WC composites is examined in 1 M KOH solution. The structure, surface morphology and surface composition is investigated using the scanning electron microscopy, X-ray diffraction and X-ray photoelectron spectroscopy. The electrocatalytic properties for the HER is evaluated based on the cathodic polarization, electrochemical impedance, cyclic voltammetry and chronopotentiometry methods. The obtained results prove the superior catalytic activity for the HER of Ni–Mo/WC composites to Ni–Mo alloy. The catalytic activity of Ni–Mo/WC electrodes is determined by the presence of WC nanoparticles and Mo content in the metallic matrix. The best electrocatalytic properties are identified for Ni–Mo/WC composite with the highest Mo content and the most oxidized surface among the studied coatings. The impedance results reveal that the observed improvement in the catalytic activity is the consequence of high real surface area and high intrinsic catalytic activity of the composite.     

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.     

Pt–Ni nanoparticles electrodeposited on rGO/CFP as high-performance integrated electrode for methanol oxidation

A novel carbon fiber paper loaded with reduced graphene oxide (rGO) was used as the substrate, on which Pt–Ni nanoparticles were electro-deposited as to prepare an integrated electrode by two electrochemical methods (cyclic voltammetry and square wave pulse). The electrochemical tests indicated two integrated electrodes had excellent performance towards methanol oxidation. Especially, Pt-Ni-CV(A)-rGO/CFP electrode showed the highest electrocatalytic activity, and mass activity reached 5.33 A·mg^?1_Pt, which was about 5.6 times that of the commercial Pt/C catalyst (JM). Further, after annealing under a reducing atmosphere, two electrodes exhibited completely different changes in the aspects of morphology and electrocatalytic performance. It can be attributed to the changes of element distribution and morphology of nanoparticles after annealing. The as-prepared Pt–Ni-rGO/CFPs composite electrode is promising for integrated electrode of proton exchange membrane fuel cells. This work opens an avenue for the preparation of high-performance integrated electrode.     

Electrochemical performance of metal-organic framework MOF(Ni) doped graphene

In the paper, MOF(Ni) and MOF(Ni) complex with graphene MOF(Ni)-GR(w%) are synthesized by solvothermal method. The structure, morphology and elemental composition of samples are analyzed by physical characterization such as SEM, XRD, EDS and XPS. The results show that MOF(Ni) and MOF(Ni)-GR(w%) with high crystallinity and less impurities are successfully synthesized. Different samples are loaded on the electrodes and their electrochemical performances are tested by electrochemical workstation. The results show that doping appropriate graphene in MOF(Ni) can effectively improve the electrochemical catalytic activity of the composites. When the content of graphene is 4%, MOF(Ni)-GR(4%) is of the highest electrochemical catalytic activity, its overpotential is 268 mV, the Tafel slope is 108 mV·dec^?1, and it has better electrochemical stability compared with that of Pt/C electrode. The ECSA and EIS of MOF(Ni)-GR(4%) are superior to that of MOF(Ni) in exploring the reasons for enhancing catalytic hydrogen evolution. The reason is that the addition of graphene enhances the conductivity of the composites and reduces the resistance of catalyst transportation. Moreover, the doping of graphene improves the specific surface area of the composites, and provides enough active sites for hydrogen evolution reaction (HER).     

Synergistic regulation of hydrogen adsorption/desorption via dual interfaces of Cu/Ni/Ni(OH)2 toward efficient hydrogen evolution reaction

Nickel-based catalysts have attracted tremendous attention as alternatives to precious metal-based catalysts for electrocatalytic hydrogen evolution reaction (HER) in virtue of their conspicuous advantages such as abundant reserves and high electrochemical activity. Nevertheless, a great challenge for Ni-based electrocatalyst is that nickel sites possess too strong adsorption for key intermediates H1, which severely suppresses the hydrogen-production activities. Herein, we report a hierarchical architecture Cu/Ni/Ni(OH)₂ consisting of dual interfaces as a high-efficient electrocatalyst for HER. The Cu nanowire backbone could provide geometric spaces for loading plenty of Ni sites and the formed Ni/Cu interface could effectively weakened the adsorption intensity of H1 intermediates on the catalyst surface. Moreover, the H1 adsorption could be further controlled to appropriate states by in-situ formed Ni(OH)₂/Ni interface, which simultaneously promotes water adsorption and activation, thus both Heyrovsky and Volmer steps in HER could be obviously accelerated. Experimental and theoretical results confirm that this interface structure can promote water dissociation and optimize H1 adsorption. Consequently, the Cu/Ni/Ni(OH)₂ electrocatalyst exhibits a low overpotential of 20 mV at 10 mA cm^?2 and an ultralow Tafel slope of 30 mV dec^?1 in 1.0 M KOH, surpassing those of reported transition-metal-based electrocatalysts and even the prevailing commercial Pt/C.     

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.     

Electrophoretic deposition of carbon-supported octahedral Pt–Ni alloy nanoparticle catalysts for cathode in polymer electrolyte membrane fuel cells

The advanced electrochemical catalytic activity for oxygen reduction reaction (ORR) based on the octahedral Pt–Ni alloyed catalyst has been demonstrated. However, a means of fabricating catalyst electrodes for use in PEMFCs that is cost-effective, scalable, and maintains the high activity of Pt–Ni_alloy/C has remained out of reach. Electrophoretic deposition (EPD) is a colloidal production process that has a history of successful deployment at the industrial scale. Here, we report on the facile preparation of an effective and active cathode consisting of Pt–Ni alloy loaded on the carbon cloth substrate using the electrophoretic deposition (EPD) technique, in which the optimum applied voltages and suspension pH are systematically investigated to obtain the highly porous Pt–Ni_alloy/C catalyst electrode. In a half cell test, the EPD-made Pt–Ni_alloy/C catalyst electrodes fabricated at 45 V and in a solution with a pH of 9.0 yields the best performances. On the other, as an active cathode, the EPD-made Pt–Ni_alloy/C electrodes deliver a superior performance in single cell test, with the maximum power density reaches 7.16 W/mg_Pt, ～28.1% higher than that of the spray-made Pt/C conventional electrode. The outperformance is attributed to the significantly higher porosity and surface roughness of the EPD-made electrode.     

Hydrogenation of cyclohexene catalyzed by nanoporous SPE-PtNi/C membrane electrode

Implementing large-scale synthesis of nanoporous PtNi/C catalysts for hydrogenation processes of unsaturated organic compounds under atmospheric pressure at temperatures below 100 °C is an urgent task. In this paper, a nanoporous SPE-PtNi/C membrane electrode is prepared by ion beam sputtering, ultrasonic-assisted electrochemical dealloying, and hotpressing. Special attention is paid to the analysis of the electrochemical properties, phase structure, surface morphology, active constituent distribution, and catalytic efficiency for cyclohexene hydrogenation of the produced electrode in comparison with those of commercial Pt/C catalysts. The results show that the ultrasonic-assisted electrochemical etching temperature exerts the most significant effect on the catalytic activity of the catalyst under consideration. In particular, the treatment of PtNi/C in 0.7 mol/L HClO₄ for 1.5 h at the optimized temperature of 50 °C enables one to increase the catalytic activity by 25.20% at decreasing the Pt-loading content by 88.85% compared with commercial Pt/C. Furthermore, the nanoporous structure of the PtNi/C surface allows the binding energy of Pt 4f_7/2 to be reduced by 0.23 eV due to the Ni loss and the crystal plane shrinkage from NiPt, which enhances the compressive strain of the lattice structure of exposed Pt and increases the number of active sites. Finally, the use of a nanoporous SPE-PtNi/C membrane electrode could increase the yield of cyclohexene during the hydrogenation reaction by 179% at simultaneously improving the current efficiency by 69%.     

Noble fabrication of Ni–Mo cathode for alkaline water electrolysis and alkaline polymer electrolyte water electrolysis

Among the catalysts for hydrogen evolution reaction (HER) in alkaline media, Ni–Mo turns out to be the most active one. Conventional preparations of Ni–Mo electrode involve repeated spraying of dilute solutions of precursors onto the electrode substrate, which is time-consuming and usually results in cracking and brittle electrodes. Here we report a noble fabrication of Ni–Mo electrode for HER. NiMoO₄ powder was synthesized and used as the precursor. After reduction in H₂ at 500 °C, the NiMoO₄ powder layer was converted to a uniform and robust electrode containing metallic Ni and amorphous Mo(IV) oxides. The distribution of Ni and Mo components in this electrode is naturally uniform, which can maximize the interaction between Ni and Mo and benefit the electrocatalysis. The thus-obtained Ni–Mo electrode exhibits a very high catalytic activity toward the HER: the current density reaches 700 mA/cm² at 150 mV overpotential in 5 M KOH solution at 70 °C. This new fabrication method of Ni–Mo electrode is not only suitable for alkaline water electrolysis (AWE), but also applicable to the alkaline polymer electrolyte water electrolysis (APEWE), an emerging technique for efficient production of H₂.     

Hydrogen evolution reaction in PTFE bonded Raney-Ni electrodes

This study is concerned with the hydrogen evolution reaction (HER) in several PTFE bonded Raney-Ni electrodes as function of temperature and treatments. The Mo-doped Raney-Ni catalysts are activated by hours of long cathodic polarization interleaved with few deep “charge - discharge” (polarity reversal) cycles. Moreover, the HER efficiency of the electrode requires additives which enhance conductivity and surface properties: with powders of Ni alloys (Ni-Ti, Ni-Cr, Ni-Fe) the electrode becomes also more stable, and almost insensitive to polarity reversal. The main effect of a temperature increase is the reduction of the Tafel slope, which is about 120 mV/dec at 25 °C, and about 60 mV/dec at 60 °C. A proper choice of additives yield electrodes which withstand polarity reversal and may be used in electrolysers which are intermittently operated, or have anodes which require periodic in situ re-activation by reduction.     

Electrocatalysis property of CuZn electrode with Pt and Ru decoration

Electrocatalysis properties strongly depend on the interaction of metallic particles and this interaction enables to change the electronic structure of alloys which enhances the catalytic activity. This property is the key factor in the developing of cost-effective and efficient Hydrogen Evolution Reaction (HER) electrocatalysts for sustainable hydrogen production. In this study, novel electrocatalysts which are decorated with Pt and Ru have been developed for HER electrocatalysis. Microscopic analysis such as scanning electron microscopy (SEM), energy dispersive X-ray (EDX), X-ray diffraction (XRD) and atomic force microscopy (AFM) are performed to determine the morphological and compositional structures. Electrocatalysis properties are evaluated by cathodic current-potential curves, electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) in 1.0 M KOH solution. Chronoamperometry (CA) and cycle tests are used for stability/durability of electrocatalysts. Results show that a small onset potential of the porous Cu/Ni/CuZn–Pt is obtained for HER. Exchange current density and polarization resistance are found to be 5.39 mA cm^?2 and 2.0 Ω cm² at overpotential of ?100 mV for porous Cu/Ni/CuZn–Pt, respectively, indicating that Cu/Ni/CuZn–Pt is higher electrocatalytic properties than the others. Moreover, very low overpotentials at 10 and 40 mA cm^?2 are obtained on porous Cu/Ni/CuZn–Pt compared with porous Cu/Ni/CuZn–Ru and Cu/Ni/CuZn. Porous Cu/Ni/CuZn–Pt also displays excellent stability/durability in test solution. The remarkable electrocatalysis properties of porous Cu/Ni/CuZn–Pt can be explained due to high porous structure, leaching of Zn from the deposit, intrinsic activity of Pt as well as changing in the electronic structure. It should be considered that porous Cu/Ni/CuZn–Pt is of high corrosion resistance in test solution for 120 h, which makes it good candidate for HER.     

Synthesis and electrocatalytic hydrogen evolution performance of Ni–Mo–Cu alloy coating electrode

Ni–Mo–Cu alloy coating electrode was prepared on copper substrate by constant current electrodeposition and characterized by scanning electron microscopy (SEM) and X-ray diffractometry (XRD). The electrochemical characterization for hydrogen evolution reaction (HER) was investigated by cyclic voltammetry (CV) curves, linear sweep voltammetry (LSV) curves and electrochemical impedance spectroscopy (EIS) techniques. Parameters affecting the electrocatalytic activity for the HER are systematically investigated. Results show the Ni–Mo–Cu coating by the introduction of Cu has a rough and cauliflower-like structure and presents a most efficient activity for HER in comparison with binary Ni–Mo electrode. Its remarkably enhanced catalytic activity is attributed to the high surface area as well as synergistic interaction between Ni, Mo and Cu.     

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.     

Optimization and characterization of pulse electrodeposited nickel selenide nanostructure as a bifunctional electrocatalyst by response surface methodology

The electrocatalytic activity of the pulse electrodeposited Ni–Se coating on nickel foam (NF) for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) was optimized by design of experiments. In this study as the first step of optimization, the condition of electrodeposition bath containing the ratio of Se/Ni, pH, and temperature was optimized. The response surface methodology (RSM) in central composite design (CCD) was used for experiments based on the parameters of the ratio of Se/Ni and pH. The prediction model after carrying out the analyses of variance (ANOVA) on the responses showed the best desirable values for the ratio of Se/Ni and pH were 0.7 and 3.6. The nanostructure Ni–Se electrode electrodeposited in the optimal condition requires 103 and 249 mV (vs. RHE) for delivering 10 mA/cm² in HER and OER, respectively. To temperature survey, the optimized Ni–Se electrode was synthesized at 25, 40, and 60 °C. Results showed that the electrode electrodeposited at the ambient temperature with large electrochemically active surface area of 8960 and low Tafel slopes of 86 and 35 mV/dec has the superior electrocatalytic performance for HER and OER, respectively.     

C16MI.OTf ionic liquid on Pt/C and PtMo/C anodes improves the PEMFC performance

The effect of 1-hexadecyl-3-methylimidazolium trifluoromethanesulfonate (C₁₆MI.OTf) ionic liquid (IL) on the catalytic activity of Pt/C or PtMo/C anodes is studied in a proton exchange membrane fuel cell (PEMFC). PtMo nanoparticles (NPs) are synthesized with two different Pt:Mo proportions (13 or 31 at.% Mo) by a borohydride method on the carbon support. The composition, crystalline structure, morphology of the PtMo/C are evaluated by energy-dispersive X-ray spectroscopy, X-ray diffraction and transmission electron microscopy, respectively. The stability tests of the electrocatalysts are carried out in acid medium using cyclic voltammetry measurements. Pt/C or PtMo/C electrocatalysts containing C₁₆MI.OTf are assessed in the anode in a H₂/air PEMFC by polarization curve and ac electrochemical impedance spectroscopy. The synthesized PtMo nanoparticles show spherical shape and average particle size of 3.5 nm. The PEMFC performance of PtMo (13 at.% Mo) at anode is very similar than of Pt/C anode. The presence of 15 wt% C₁₆MI.OTf in the Pt/C or PtMo/C (13 at.% Mo) anodes let to an increase of the maximum power values, 71 and 107 W g_Pt^?1 cm^?2, respectively. The catalytic surfaces of nanoparticles are modified due to C₁₆MI.OTf presence which improved the PEMFC performance. This result agrees with the EIS analysis, where the resistances of charge transfer and mass transfer decrease in the C₁₆MI.OTf presence. However, this effect is more pronounced for PtMo/C (13 at.% Mo) catalyst, demonstrate that PtMo/C anodes with a small amount of Mo and C₁₆MI.OTf ionic liquid improve significantly the PEMFC performance.     

Ni–Cr alloys for effectively enhancing hydrogen evolution processes in phosphate-buffered neutral electrolytes

Significant efforts have been made to develop highly active non-noble metal-based, affordable metallic and stable electro-catalysts for hydrogen evolution reaction (HER). Strong acid and bases are now used in HER operations to achieve large-scale, sustained H₂ fuel production. However, few studies have utilized phosphate-buffered neutral electrolytes (PBS) in the field of neutral electrolyte technology. In this work, a certain alloys with a Ni–Cr basis have been produced as favorable components for the HER under neutral conditions. Additionally, the current investigations are emphasizing on the concentration of buffer phosphate species in the HER activity of various materials. By employing polarization and electrochemical impedance spectroscopy (EIS) in neutral solutions, the electro-catalytic activity of new alloys on HER was evaluated. According to the preliminary findings, the examined Ni–Cr-based alloys show superior HER catalytic activity in neutral electrolytes. Additionally, the Ni–Cr alloy matrix with Fe and Mo added enhances HER electrocatalytic efficiency while lowering interfacial charge transfer resistance. Due to its low overpotential of ?297 mV @ 10 mA cm^?2 and Tafel slope of 94 mV dec^?1 in 1.0 M PBS media, the Ni–Cr–Mo–Fe alloy exhibits an efficient HER, suggesting that the Ni–Cr–Mo–Fe electrode will be a potential noble metal-free electro-catalyst for HER. The Ni–Cr–Mo–Fe cathode is a readily available and affordable material for the production of HER in neutral medium.     

Pulse-microwave assisted polyol synthesis of highly dispersed high loading Pt/C electrocatalyst for oxygen reduction reaction

In the present investigation, a high loading Pt/C up to 50% (weight ratio) was prepared by a pulse-microwave assisted polyol synthesis method, in which the metal reduction can be accomplished in 2 min. X-ray diffraction (XRD) and transmission electron microscopy (TEM) results showed that the Pt particles were highly dispersed on the support and had a narrow particle distribution with a mean particle size of about 2.7 nm. Based on the electrochemical properties characterized by cyclic voltammetry and rotating disk electrode techniques, it was found that the as-prepared 50% Pt/C exhibited a comparable activity for oxygen reduction reaction with respect to the commercial one.     

Highly durable,Pt free and large-area Ni–B film synthesized by SILAR as a bifunctional electrode for electrochemical water splitting

A search for efficient, durable, large-area, and economic catalyst material for low-cost production of hydrogen and oxygen is currently a high priority in the field of electrocatalysis (EC). In view of this, a cost-effective, earth abundant, highly stable, Pt free, and large-area (8 cm × 8 cm) bifunctional Ni–B electrocatalyst is reported via simple and economic SILAR method. A highly porous surface of Ni–B film with high surface wettability indicated better electrochemical water-splitting properties for the films and is obtained at 100 cycles. A Low over-potential value to obtain HER (49 mV) and OER (340 mV) at 10 mA/cm² current suggested that they are comparable to the well-known Pt and RuO electrodes in alkaline medium (1M KOH), respectively. In actual water-splitting setup having Ni–B film (as cathode) and stainless steel (as anode), the hydrogen production of 612 ml/h is obtained at constant potential, which was enhanced by 18% i.e., 726 ml/h when a Ni–B film as both cathode and anode electrode was used. Both the electrodes are highly stable for over 15 days and interestingly they showed 7% increment in the EC performance.