Facile aqueous phase synthesis of 3D-netlike Pd–Rh nanocatalysts for methanol oxidation

The structure-activity relationship between the morphology and composition of Pd-based nanocatalysts is an important fundamental issue in direct methanol fuel cells (DMFC). Three dimensional (3D) netlike Pd–Rh bimetallic catalysts with different atomic ratios (Pd₁Rh₃, PdRh, Pd₃Rh₁) are synthesized through a simple wet chemical way using P123 as a reducing agent and KBr as morphological regulator. The morphology, structure and composition of the catalysts are proved by a series of physicochemical test technology. It is shown that the 3D-netlike structure is composed of short self-assembly nanochains. Electrochemical results display that their application towards methanol oxidation reaction (MOR) in alkaline solution. The MOR activity of the optimized Pd₃Rh₁ nanocatalyst is improved to about 4.0 mA cm⁻², which is much higher than that of the commercial Pd/C catalyst.     

Performance evaluation of molybdenum dichalcogenide (MoX2; X= S,Se, Te) nanostructures for hydrogen evolution reaction

Hydrogen evolution reaction (HER) using transition metal dichalcogenides (TMDs) have gained interest owing to their low-cost, abundancy and predominant conductivity. However, forthright comparisons of transition metal chalcogenides for HER are scarcely conducted. In this work, we report the synthesis of series of molybdenum chalcogenide nanostructures MoX₂ (X = S, Se, Te) via a facile hydrothermal method. Used as an electrocatalyst for HER, MoS₂ nanograins, MoSe₂ nanoflowers and MoTe₂ nanotubes could afford the benchmark current densities of 10 mA cm⁻² at the overpotentials of −173 mV, −208 mV and −283 mV with the measured Tafel slope values of 109.81 mV dec⁻¹, 65.92 mV dec⁻¹ and 102.06 mV dec⁻¹, respectively. Besides other factors influencing HER, the role of electronic conductivity in HER of these molybdenum dichalcogenides are elucidated. In addition, the presented molybdenum dichalcogenides in this work are also complimented with robustness as determined from high-current density stability measurements.     

A novel co-electrodeposited Co/MoSe2/reduced graphene oxide nanocomposite as electrocatalyst for hydrogen evolution

In this study, a simple and fast electrochemical method was employed to synthesis molybdenum diselenide thin film. The morphology, structure and chemical composition of the nanocomposites were investigated by field emission scanning electron microscopy, X-ray diffraction, energy dispersive X-ray spectroscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. The progressive effects of transition metal ions including Ni, Cu, and Co were surveyed on the hydrogen evolution activity of MoSe₂ thin films. Co/MoSe₂ nanocomposite thin films has significant electrocatalytic activity as compared to other samples, In order to achieve higher performance, preparing Co/MoSe₂/RGO nanocomposite thin film, two strategies including layer by layer electrodeposition and co-electrodeposition has been employed. The presence of reduced graphene oxide leading to the onset potential shifts to more positive values and increase the current density. Also, results showed that the Co/MoSe₂/RGO nanocomposite prepared by co-electrodeposition exhibits the best electrochemical hydrogen evolution at onset potential of −0.18 with an overpotential of −0.45 V.     

Sequential hydrothermal synthesized Co–Mn-oxide/C electrocatalysts for oxygen reduction in alkaline media

In order to design and synthesize oxygen reduction reaction catalysts with high activity and low cost, a series of Co–Mn-oxide/C catalysts with different Co:Mn ratios have been prepared using a hydrothermal method applied in sequential steps. The monotonically systematic trends of the catalysts’ phases, morphologies and particle sizes have been verified, and the trending of Mn ions and Co ions in different valence states follows the increasing Co:Mn ratio. Electrochemical performance of the catalysts in oxygen reduction reaction results in a volcano-type trend with an optimal Co:Mn ratio of 3 giving the best performance, which is comparable to that of commercial Pt/C. Lastly, a Koutecky-Levich approach has been employed to deduce the electron transfer values, in an attempt to rationalize their selectivity towards the varying 2 and 4 electron pathways. The systematic research is significant for understanding and designing a new generation of non-noble metal oxygen reduction reaction catalysts.     

Facile one-step fabrication of bimetallic Co–Ni–P hollow nanospheres anchored on reduced graphene oxide as highly efficient electrocatalyst for hydrogen evolution reaction

It is significant but challenging to develop noble-metal-free electrocatalysts exhibiting high activity and long-term stability toward hydrogen evolution reaction (HER) to satisfy the ever-increasing demand for clean and renewable energy. Herein, an environment-friendly and low-temperature electroless deposition method is developed for the synthesis of Co–Ni–P hollow nanospheres anchored on reduced graphene oxide nanosheets (Co–Ni–P/RGO). By optimizing the molar ratio of Ni/Co precursor, composition dependent electrocatalytic performances toward HER of nanostructured Co–Ni–P/RGO electrocatalyst are investigated in 1.0 M KOH solution. The results suggest that when the molar ratio of Ni/Co precursor is 3/7, as-prepared ternary Co–Ni–P/RGO electrocatalyst exhibits a remarkably enhanced HER activity in comparison to binary Ni–P/RGO and Co–P/RGO electrocatalysts, delivering a current density of 10 mA cm⁻² at the overpotential of only 207 mV. The value of Tafel slope for nanostructured Co–Ni–P/RGO electrocatalyst reveals that HER process undergoes Volmer-Heyrovsky mechanism. Besides, nanostructured Co–Ni–P/RGO electrocatalyst features superior stability under alkaline condition. The results suggest that nanostructured composite of Co–Ni–P hollow nanospheres/RGO is a potential candidate for hydrogen production through water splitting.     

Cobalt oxide nanocomposites and their electrocatalytic behavior for oxygen evolution reaction

In this work, we have described the simple preparation method of cobalt oxide nanocomposites where cobalt oxide nanoparticles were grown on the surface of carbon nanotube, graphene oxide and graphene (Co₃O₄@CNT, Co₃O₄@GO, Co₃O₄@G). The as-grown Co₃O₄@CNT, Co₃O₄@GO, Co₃O₄@G were investigated for H₂O oxidation. The nanoparticles displayed high activity toward oxygen evolution. Further, the stability of the catalysts were tested in alkaline solution, which exhibited good stability. Among all nanoparticles, Co₃O₄@G exhibited higher current density at lower overpotential and also exhibited lower Tafel slope (157.1 mV dec⁻¹) as compared to Co₃O₄@CNT and Co₃O₄@GO. The Co₃O₄@G delivered a current density of 10 mAcm⁻² at 0.8 V (overpotential 535 V versus Ag/AgCl) in 0.1 M KOH solution, which is superior than many electrocatalysts reported for oxygen evolution so far. The good electrocatalytic performance might be due to the structural features of Co₃O₄@G, which cause enhancement of oxygen evolution activity.     

Superior hydrogen evolution electrocatalysis enabled by CoP nanowire array on graphite felt

Renewable electricity-powered hydrogen production is an attractive alternative to unsustainable industrial processes, but the large-scale implantation of such sustainable technology still requires efficient and noble-metal-free electrocatalysts for driving cathodic hydrogen evolution reaction (HER), especially under alkaline conditions. In this paper, CoP nanowire array was in-situ developed on porous graphite felt (CoP/GF) as a new 3D electrocatalyst in facilitating hydrogen evolution electrocatalysis. This CoP/GF presents outstanding HER activity, requiring a low overpotential of 130 mV to deliver a current density of 20 mA cm^?2 as tested in 1.0 M KOH. Furthermore, this free-standing catalyst exhibits impressive long-term durability of up to 50 h under working conditions.     

Structure engineering of amorphous P–CoS hollow electrocatalysts for promoted oxygen evolution reaction

Oxygen evolution reaction (OER) is a key process involved in many energy-related conversion systems. An ideal OER electrocatalyst should possess rich active sites and optimal binding strength with oxygen-containing intermediates. Although numerous endeavors have been devoted to the modification and optimization of transition-metal-based OER electrocatalysts, they are still operated with sluggish kinetics. Herein, an ion-exchange approach is proposed to realize the structure engineering of amorphous P–CoS hollow nanomaterials by utilizing the ZIF-67 nanocubes as the precursors. The precise structure control of the amorphous hollow nanostructure contributes to the large exposure of surface active sites. Moreover, the introduction of phosphorus greatly modifies the electronic structure of CoS₂, which is thus favorable for optimizing the binding energies of oxygenated species. Furthermore, the incorporation of phosphorus may also induce the formation of surface defects to regulate the local electronic structure and surface environment. As a result of this, such P–CoS hollow nanocatalysts display remarkable electrocatalytic activity and durability towards OER, which require an overpotential of 283 mV to afford a current density of 10 mA cm^?2, outperforming commercial RuO₂ catalyst.     

Revealing the role of Ni2+ ions in inducing the synthesis of porous carbon balls: A novel substrate to enhance the Pt catalytic activity towards methanol-oxidation

Carbon-based materials have been often employed as electrocatalytic substrates because of their large surface area/highly porous structure. Similar to carbon substrates, the non-carbon related materials such as transition metals also play an important role in improving catalytic performance. However, the simultaneous synthesis and metallic functionalization of carbon substrates is a highly challenging issue. Herein, a hydrothermal method has been used for the preparation of Ni-functionalized porous carbon balls. The significant role of Ni²⁺ ions in the synthesis of porous carbon balls has been confirmed. The results of transmission electron microscopy indicate that, the as-prepared porous carbon balls were suitable for the dispersion of Pt nanoparticles with small particle size (less than 4 nm). In addition to providing the OH_ads species, the Ni can also modify the surface electronic structure of Pt. Electrochemical measurements results reveal that, under the strong interactions between Ni and Pt, the as-prepared porous carbon balls supported Pt nanoparticles (Pt/Ni-CB) catalyst possesses excellent electrocatalytic activity, stability and CO anti-poisoning capability towards methanol electrooxidation reaction (MOR). This work opens a novel idea for the construction of the metal functionalization of carbon substrates and their subsequent applications in other electrocatalytic reactions.