High activity PtPd-WC/C electrocatalyst for hydrogen evolution reaction

Pd modified Pt over a novel support of tungsten carbide nanocrystals (the catalyst denotes as PtPd-WC/C) have been prepared by using an intermittent microwave heating (IMH) method. The as-prepared electrocatalysts are characterized by using the techniques of XRD, SEM, TEM, linear sweeping voltammetry and tested for the hydrogen evolution reaction (HER) in the acidic media. It shows a better performance for the HER on PtPd-WC/C electrocatalyst than that on Pt-WC/C electrocatalyst. In addition, these effects on the catalytic activity by changing environmental temperature and electrolyte concentration were taken into account. Kinetic study shows that the HER on the PtPd-WC/C electrocatalyst gives higher exchange current density in H₂SO₄ solution with high concentration, leading to a lower overpotential and facile kinetics. XRD, SEM and TEM images of PtPd-WC/C show the crystalline features of Pt, Pd and tungsten carbides and indicated the coexistence of these components.     

Transition metal carbides coupled with nitrogen-doped carbon as efficient and stable Bi-functional catalysts for oxygen reduction reaction and hydrogen evolution reaction

Developing non-precious metal catalysts for oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER) is crucial for proton exchange membrane fuel cell (PEMFC), metal-air batteries and water splitting. Here, we report a in-situ simple approach to synthesize ultra-small sized transition metal carbides (TMCs) nanoparticles coupled with nitrogen-doped carbon hybrids (TMCs/NC, including WC/NC, V₈C₇/NC and Mo₂C/NC). The TMCs/NC exhibit excellent ORR and HER performances in acidic electrolyte as bi-functional catalysts. The potential of WC/NC at the current density of 3.0 mA cm^?2 for ORR is 0.814 V (vs. reversible hydrogen electrode (RHE)), which is very close to Pt/C (0.827 V), making it one of the best TMCs based ORR catalysts in acidic electrolyte. Besides, the TMCs/NC exhibit excellent performances toward HER, the Mo₂C/NC only need an overpotential of 80 mV to drive the current density of 10 mA cm^?2, which is very close to Pt/C (37 mV), making it the competitive alternative candidate among the reported non-precious metal HER catalysts.     

N-doped graphene supported W2C/WC as efficient electrocatalyst for hydrogen evolution reaction

Tungsten carbides (W₂C and WC) materials, as promising non-precious electrocatalysts, possess highly efficient activity for HER. Herein, N-doped graphene supported tungsten carbide (N–W₂C/WC) nanocomposite is synthesized by spray drying process followed with a two-step pyrolysis treatment, which exhibits a remarkable hydrogen evolution reaction (HER) activity and excellent stability in acidic solution and alkaline solution. N–W₂C/WC displays low overpotentials of 166 mV and 125 mV to achieve a current density of 10 mA cm^?2 and small Tafel slopes of 60.97 and 62.66 mV dec^?1 in 0.5 M H₂SO₄ and 1.0 M KOH, respectively. After 1000 cycles, the electrocatalytic activity of N–W₂C/WC is almost no change in acidic media but slightly decreases in alkaline media. This work might provide a new way to explore high comprehensive performance tungsten-based electrocatalyst for HER.     

Edge-halogenated graphene nanosheets as an efficient metal-free electrocatalyst for hydrogen evolution reaction

Application of carbonic materials as catalysts has recently been considered due to some advantages like tunable molecular structures, easy synthesis methods, abundance, and high tolerance in acidic and alkaline media. Here, a new metal-free electrocatalyst of halogenated reduced graphene oxide was prepared using cyclic voltammetry X (F, Br, and I)-RGO electrodeposition method. The prepared electrocatalysts were studied as a novel metal-free electrocatalyst for the hydrogen evolution reaction, and the presence of several halogen and oxygen functional groups on the surface of nanosheets was verified by the furrier transform infra-red, FT-IR, spectroscopy, and the presence of doped halogens on the RGO surface was confirmed by energy-dispersive X-ray, EDX, spectroscopy. The structural features and surface morphology of electrocatalysts were investigated by scanning electron microscopy (SEM) analysis. The electrochemical treatment of the X (F, Br, I)-RGO electrode was studied by some techniques like electrochemical impedance spectroscopy, EIS, chronoamperometry, CA, and linear sweep voltammetry, LSV. The X (F, Br, I)-RGO catalyst showed a lower onset potential (?0.81 V. vs. SHE), higher exchange current density (3.1 × ×10^?1 mA cm^?2), and lower charge transfer resistance (1.09 Ω cm²) related to the RGO catalyst due to the high active sites by heteroatoms and graphene nanosheets.     

High active and easily prepared cobalt encapsulated in carbon nanotubes for hydrogen evolution reaction

We prepared M/CeO₂ (M = Fe, Co or Ni) by coprecipitation method, and then fabricated M@CNT/CeO₂ electrocatalysts through ethanol decomposition on M/CeO₂. Experimental results showed that the activity of Co@CNT/CeO₂ for hydrogen evolution reaction (HER) was much higher than that of Fe@CNT/CeO₂ and Ni@CNT/CeO₂, these experimental results were consistent with the density functional theory (DFT) calculation results. The electrocatalysts from ethanol decomposition on Co/CeO₂ at 800 °C with different time were obtained, and their electrocatalytic activities for HER were discussed. Co@CNT-90 showed higher activity than others, when the reaction time exceeded 90 min, their HER activities declined gradually, because long-term ethanol decomposition caused decreased dispersion and thicker layers of carbon nanotube (CNT). To obtain a current density of 10 mA cm⁻², overpotential of 181 mV was required for Co@CNT-90, and its polarization curve after 8000 cycles retained a similar performance to the initial polarization curve. The high activity and durability of Co@CNT-90 could be explained from the carbon-encapsulated-metal structure, thus metal was protected by carbon layers and prevented metal from contacting with electrolyte directly. XRD patterns, TEM images and experimental results proved that Co was well encapsulated by CNT.     

Electrochemically assisted synthesis of three-dimensional FeP nanosheets to achieve high electrocatalytic activity for hydrogen evolution reaction

Iron phosphide (FeP) is a promising alternative catalyst for electrocatalytic hydrogen evolution reaction (HER) due to its low price, highly active catalytic sites and long-term anti-acid corrosion. Herein, we report a very facile strategy to fabricate novel FeP nanosheets as a HER electrocatalyst. Three-dimensional interconnected nanosheet structures of Fe₂O₃ (3D Fe₂O₃ NS) were directly exfoliated from metal Fe wires by alternating current (AC) voltage disturbance, and a simple subsequent phosphorization process could easily convert γ-Fe₂O₃ into FeP phase, which also maintained the 3D NS structure. Importantly, increasing the AC voltage resulted in the evolution of iron-containing nanostructures from nanoparticles to 2D nanosheets until the formation of 3D NS structure. Owing to the large specific surface area, enriched active sites and abundant hierarchical porous channels, as-prepared 3D FeP NS has exhibited significantly enhanced electrocatalytic HER activities such as a cathode current density of 10 mA cm⁻² at a small overpotential of 88 mV, low Tafel slope (47.7 mV dec⁻¹) and satisfactory long-term stability in acidic electrolyte. We expect that this simple and green synthetic strategy of transition metal phosphides will provide a promising prospect to innovate nonprecious HER electrocatalysts.     

Co/Mo2C composites for efficient hydrogen and oxygen evolution reaction

Non-precious transition metal electrocatalysts with high catalytic performance and low cost enable the scalable and sustainable production of hydrogen energy through water splitting. In this work, based on the polymerization of CoMoO₄ nanorods and pyrrole monomer, a heterointerface of carbon-wrapped and Co/Mo₂C composites are obtained by thermal pyrolysis method. Co/Mo₂C composites show considerable performance for both hydrogen and oxygen evolution in alkaline media. In alkaline media, Co/Mo₂C composites show a small overpotential, low Tafel slope, and excellent stability for water splitting. Co/Mo₂C exhibits a small overpotential of 157 mV for hydrogen evolution reaction and 366 mV for oxygen evolution reaction at current density of 10 mA cm⁻², as well as a low Tafel slope of 109.2 mV dec⁻¹ and 59.1 mV dec⁻¹ for hydrogen evolution reaction and oxygen evolution reaction, respectively. Co/Mo₂C composites also exhibit an excellent stability, retaining 94% and 93% of initial current value for hydrogen evolution reaction and oxygen evolution reaction after 45,000 s, respectively. Overall water splitting via two-electrode water indicates Co/Mo₂C can hold 91% of its initial current after 40,000 s in 1 M KOH.     

Highly efficient and durable phosphine reduced iron-doped tungsten oxide/reduced graphene oxide nanocomposites for the hydrogen evolution reaction

The design and development of inexpensive and highly efficient electrocatalysts for hydrogen production from water splitting are highly crucial for green energy and the hydrogen economy. Herein, we report phosphine reduced an iron-doped tungsten oxide nanoplate/reduced graphene oxide nanocomposite (Fe-WOxP/rGO) as an excellent electrocatalyst for the hydrogen evolution reaction. This electrocatalyst was synthesized using a hydrothermal method, followed by reduction with phosphine (PH₃), which was generated from sodium hypophosphite. The catalyst onset potential, Tafel slope, and stability were investigated. Accordingly, Fe-WOxP/rGO exhibited impressively high electrocatalytic activity with a low overpotential of 54.60 mV, which is required to achieve a current density of 10 mAcm^?2. The Tafel slope of 41.99 mV dec^?1and the linear sweep voltammetry curve is almost the same as 2000 cycles and electrolysis under static overpotential (54.60 mV) is remain for more than 24 h in 0.5 M H₂SO₄. The catalytic activity and conductivity of Fe-WOxP/rGO were higher than WO_XP, Fe-WOxP and WOxP/rGO. Such an outstanding performance of the Fe-WOxP/rGO nanocomposite is attributed to the coupled synergic effect between high oxygen vacancies formation on tungsten oxide in the nanoplate-like structure of Fe-WOxP and rGO nanosheet, making it as an excellent electrocatalyst for hydrogen evolution reaction.     

Porous molybdenum carbide microspheres as efficient binder-free electrocatalysts for suspended hydrogen evolution reaction

Generally, the electrocatalysts are immobilized on conductive electrodes or in-situ grown on current-collecting substrates, which causes some disadvantages. For the first time, the obtained porous molybdenum carbide microspheres with diameters of 200–400 μm are employed as binder-free electrocatalysts in the novel model of suspended hydrogen evolution reaction (SHER), which possess the perfect catalytic stability and high practicability. Herein, porous molybdenum carbide microspheres synthesized by ion exchange reaction and subsequent calcining process are employed as electrocatalysts for HER, which possess a low onset potential of ?79 mV vs. RHE and a low overpotential of 174 mV achieving a current density of 10 mA/cm² in 0.5 M H₂SO₄. This work may provide a new methodology for rational design and fabrication of reaction pattern for the electrolysis of water.     

Three-demensional NiCoNiCo2O4/NF as an efficient electrode for hydrogen evolution reaction

At present, there is an urgent need for plentiful non-noble metal catalyst to substitute for valuableness platinum based metal catalyst in electrochemical water splitting. Here, we fabricated a three-demensional (3D) NiCoNiCo₂O₄ nanosheets electrocatalyst that directly grew on Ni foam firstly and then were reduced in 0.1 mol dm⁻³ sodium borohydride solution. This electrode exhibited high activity in 1.0 mol dm⁻³ KOH solution with an onset potential of ∼40 mV and a tafel slope of 77 mV dec⁻¹. Furthermore, the NiCoNiCo₂O₄/NF electrode showed a splendid durability during long-playing electrochemical test. Our work may provide an inexpensive, easy-to-obtain and excellent catalyst candidate for future electrolytic water research and industry studies that may involve hydrogen applications in the future.     

CoNi alloy nanoparticles coated with carbon layer doped with P atom for efficient hydrogen evolution reaction

Low cost, high activity and stability electrocatalysts for hydrogen evolution reaction (HER) have been extensively studied in recent years. We have successfully synthesized a transition metal phosphide electrocatalyst (CoNi@CP) with coating structure. The CoNi@CP was prepared with the mild conditions. An organophosphorus ligand was synthesized by simple organic reaction. It was synthesized by coordination with Co²⁺ and Ni²⁺ and then calcined. CoNi@CP has abundant and uniform phosphorus atom doping, no energy consumption in phosphating process, and avoids the generation of highly toxic gas PH₃. Because of its special coating structure, the adsorption of H¹ on its surface was enhanced, and the active center of CoNi was protected, which contributed greatly to the improvement of catalytic performance. At 10 mA/cm² current density, the overpotential of the catalyst only 74 mV, and the slope of Tafel was only 83 mVdec^-1. The performance of the catalyst remained unchanged after 1000 stability tests. In addition, we had proved theoretically that the catalyst had high HER activity by DFT calculation. Therefore, it provides inspiration for us to better develop efficient transition metal phosphide electrocatalysts.     

Highly efficient Ni0.5Fe0.5Se2/MWCNT electrocatatalyst for hydrogen evolution reaction in acid media

In the present energy scenario of the world, hydrogen with high energy content seems to be a better green alternative to depleting fossil fuels. Here we describe an innovative and efficient iron nickel diselenide (Ni_0.5Fe_0.5Se₂) as a potential electrocatalyst for hydrogen evolution reaction in acid media. Ni_0.5Fe_0.5Se₂ has been fabricated by means of one-step hydrothermal process supported by multi walled carbon nanotubes (MWCNTs). Ni_0.5Fe_0.5Se₂/MWCNTs electrocatalyst has been prepared from cost-effective and highly available earth-abundant elements. The crystalline structure, morphology and elemental composition of Ni_0.5Fe_0.5Se₂/MWCNTs with different weight percentage (1, 3, 5, 7%) of MWCNTs in the composite. The electrocatalysts has been successfully evaluated by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), energy dispersive X-ray analysis (EDAX), field emission scanning electron microscopy (FE-SEM). Cyclic voltammetry (CV), Tafel and electrochemical impedance analysis have been utilized to investigate. Among the investigated weight percentages, the electrocatalyst with 3 wt% of MWCNT exhibited high hydrogen evolution activity with a current density of 10 mA/cm² at an overpotential 200 mV with a Tafel slope of 71 mVdec⁻¹. The synergistic efforts between Ni_0.5Fe_0.5Se₂ and MWCNTs in the promotion of hydrogen evolution activity is ascribed to active sites, low electron transfer resistance and superior electrochemical kinetics of molecular hydrogen (H₂) production.     

Novel one-step synthesis of nickel encapsulated carbon nanotubes as efficient electrocatalyst for hydrogen evolution reaction

In this work, we report the synthesis of Ni nanoparticles encapsulated in carbon nanotubes (CNTs) by a facile and novel one-step pyrolysis method which are obtained from fumaric acid and nickel acetate as carbon and nickel sources respectively. The synthesized Ni encapsulated CNTs were characterized by various methods and were confirmed to possess large surface areas and numerous mesopores, they were applied as non-precious metal electrocatalyst for HER in 1 M KOH solution. The results show that the Ni encapsulated carbon nanotubes synthesized at 650 °C exhibited the best catalytic activity and stability with the smallest Tafel slope of 102 mV dec⁻¹, an onset potential of 110 mV and overpotential of 266 mV to achieve a current density of −10 mA cm⁻².     

Cobalt nanoparticles encapsulated in nitrogen-rich carbonitride nanotubes for efficient and stable hydrogen evolution reaction at all pH values

Developing non-precious and high-efficiency Pt free electrocatalysts for the hydrogen evolution reaction (HER) in both acid and base remained as a significant challenge. Herein, a novel Co nanoparticles encapsulated in nitrogen-rich carbonitride (Co@Co–N–C) electrocatalyst was fabricated via a facile approach of melamine polymerization and Co²⁺ in situ deposition and reduction. The optimized Co@Co–N–C catalyst demonstrates outstanding catalytic activity for HER in a wide range pH values. In particular, it shows ultralow onset potentials of 62 mV and 46 mV and overpotentials of 178 mV and 157 mV to achieve current density of 10 mA cm^?2 in acidic and alkaline media, respectively. Moreover, it presents outstanding electrochemical durability without degradation at all pH values. Such highly efficient electrocatalytic performance is mainly attributed to the maximum of synergistic effects between uniform dispersed Co nanoparticles and N-rich carbonitride nanotubes.     

Ruthenium-manganese phosphide nanohybrid supported on graphene for efficient hydrogen evolution reaction in acid and alkaline conditions

Transition metal phosphides (TMPs) have been proved to be promising, economical and effective catalysts for hydrogen evolution reaction (HER). Precious metals with transition metals alloying can appropriately adjust the adsorption energy, which is an effective solution for greatly reducing the cost of noble metal catalysts and improving their inherent performance. Herein, a simple method was employed to synthesize MnRuPOGO-500 nano-catalysts with a particle size of about 5 nm, which showed excellent HER performance under both acid and basic media. In acidic solution, the optimal catalyst displayed the overpotential of HER to reach 10 mA cm^?2 with 109 mV, a small Tafel slope of 38.55 mV dec^?1 and long-time durability of 60 h. Especially in alkaline medium, the low overvoltage of 27 mV, a small Tafel slope of 57.35 mV dec^?1 and continuing stability of 48 h were further achieved. Meanwhile, we can find that manganese has negligible HER activity, but the doping of manganese generates a synergistic modulation effect in the MnP–Ru₂P alloy, thereby improving the HER performance of the catalyst. This paper brings a simple scheme and unique insights to the design of transition metals and platinum group metals (PGMs) phosphide alloy electrocatalysts.     

Ni foil supported FeNiP nanosheet coupled with NiS as highly efficient electrocatalysts for hydrogen evolution reaction

The investigation and development of bimetallic phosphosulphide electrocatalyst with low cost and abundant reserves is extremely significant for the improvement of the efficiency of hydrogen evolution reaction (HER), while it remains a challenge. Herein, we explored a feasible method to prepare three-dimensional (3D) self-supported FeNiP-S/NF-5 nanosheet arrays on Ni foil (NF) by hydrothermal method and in situ phosphorization and following sulfurization treatment. The as-obtained FeNiP-S/NF-5 only needs a potential of 183 mV vs. RHE to reach 20 mA cm⁻², which is smaller than that of FeNiP/NF (187 mV vs. RHE) and FeNiS/NF-5 (239 mV vs. RHE), presenting excellent electrocatalytic stability. Such outstanding performance of the FeNiP-S/NF-5 can be attributed to following several reasons: (i) bi-metallic phosphide and sulphide have the high intrinsic activity because of its synergistic effect; (ii) the 3D nanosheet arrays structure of FeNiP-S/NF-5 is conducive to expose plentiful active sites and facilitate the electrolyte penetration along with electron transportation; (iii) the sulfurization process followed phosphorization treatment could further optimize their electronic structure and inhibited the surface oxidation of catalyst in the catalytic process.     

Facile synthesis of NiS2 nanowires and its efficient electrocatalytic performance for hydrogen evolution reaction

Recently, the first-row transition metal dichalcogenides MX₂ (M = Fe, Co, Ni; X = S, Se) have been widely reported as promising catalysts for hydrogen evolution reaction (HER) because of its excellent catalytic activity and earth-abundance. The rational nanostructure designs have been proved as an effective way to improve their catalytic performance. However, the reported one dimension (1D) NiS₂ nanowires for HER suffer from a large Tafel slope. Here, we report a facile synthesis of 1D NiS₂ nanowires and its high efficient catalytic activity in HER. This nanowire structure with large surface area and active sites enables highly efficient electrocatalytic performance in HER with a much smaller Tafel slope (83.5 mV/dec) compared to that of bulk NiS₂ (136 mV/dec) as well as long-term stability. Our work builds up a structure–performance relationship and enriches the synthetic strategy to other efficient catalysts such as first-row transition metal dichalcogenides or transition metal phosphide.     

Quaternary-metal phosphide as electrocatalyst for efficient hydrogen evolution reaction in alkaline solution

Hydrogen evolution reaction (HER) is a critical process in electrocatalytic water splitting for hydrogen production. However, the development of low-cost electrocatalysts for highly efficient HER is still a huge challenge. Hence, we fabricate a multi-metal phosphide on Ni foam, FeCoNiNb_xP, through a facile hydrothermal reaction followed by phosphorization. We find that Nb promotes the formation of metal phosphides, and the main phases of the catalysts with Nb are multiphase phosphides. Importantly, the Nb incorporation significantly improves the HER activity of FeCoNiP. We show that FeCoNiNb_0.3P has the best HER activity, which only requires an overpotential of 78 mV to achieve a current density of 10 mA cm^?2 in 1 M KOH, and demonstrates excellent stability under both constant potential and varied current densities. Our findings show that the multiple-metal compounds are beneficial to the improvement of catalytic activity and provide guidance on the design of novel catalysts for applications.     

Tungsten phosphide nanosheets seamlessly grown on tungsten foils toward efficient hydrogen evolution reaction in basic and acidic media

Exploring earth-abundant electrocatalyst with active and stable hydrogen evolution reaction (HER) properties is desirable but still challengeable. Herein, WP₂ nanosheets are seamlessly grown on W foil (WP₂ NSs/W) through phosphorization of WO₃/W. This seamless WP₂/W structure is beneficial to reducing the resistance between WP₂ and W. Along with the exposed large density of active sites, WP₂ NSs/W displays outstanding HER activity with a lower onset potential of about 0 V, a smaller overpotential of 90 mV for the current density of 10 mA/cm² in basic media. Notably, WP₂ NSs/W electrode also catalyzes HER efficiently in acid. The synthesis of WP₂ NSs/W provides us a straightforward strategy to gain more cost-effective cathode for HER.