Nickel phosphide decorated Pt nanocatalyst with enhanced electrocatalytic properties toward common small organic molecule oxidation and hydrogen evolution reaction: A strengthened composite supporting effect

In this paper, well-dispersed Ni₂P-NiP₂-Pt/CNTs catalyst promoted by nickel-phosphorus compounds was readily synthesized by a two-step hydrothermal process. The as-synthesized Ni₂P-NiP₂-Pt/CNTs displayed improved electrocatalytic properties towards electro-oxidation of common small organic fuels such as methanol, ethanol and formic acid in contrast with Pt/CNTs and Pt/CNPs in acidic electrolytes. Meanwhile, the Ni₂P-NiP₂-Pt/CNTs catalyst also exhibited the excellent performance toward hydrogen evolution reaction with a more negative onset potential (?15 mV) and a smaller Tafel slope (29.8 mV dec^?1) when compared with Pt/CNTs (?29 mV, 30.6 mV dec^?1) and Pt/CNPs (?32 mV, 31.3 mV dec^?1) in 1.0 M H₂SO₄ solution. The catalytic activity enhancement possibly derives from the induced large specific surface area of carbon nanotubes as well as the strengthened synergistic effect between multiple supporting interactions.     

Novel strongly coupled tungsten-carbon-nitrogen complex for efficient hydrogen evolution reaction

Alternatives to noble metal based electrocatalysts are vitally necessary to produce hydrogen from water at low overpotentials. Earlier research on tungsten based electrocatalyst has been mainly concentrated towards tungsten carbide (WC) and tungsten nitride (WN) as the potential electrocatalysts for hydrogen evolution reaction (HER), whereas tungsten carbide (W₂C) has been least focused upon. Herein, we report a highly active novel strongly coupled tungsten-carbon-nitrogen complex (W₂C-NC-WN complex) prepared by in situ carbonization method. This W₂C-NC-WN complex exhibits a remarkable electrochemical performance for HER with a small onset potential of 33 mV vs. RHE and requires an overpotential (η) of 145 mV vs. RHE to render ?10 mA cm^?2 current density. The Tafel analysis demonstrates a slope of 96 mV dec^?1 which is much better than WN (109.6 mV dec^?1) and WC (142.4 mV dec^?1). The strong coupling of W₂C and WN within N-doped carbon (NC) framework brings about a significant enhancement in HER kinetics and faster electron transport due to the remarkable reduction in charge transfer resistance. The facile synthetic approach reported here, provides a powerful tool for the structurally controlled modification of the catalyst while simultaneously introducing active species.     

One-pot solvothermal synthesis of PdCu nanocrystals with enhanced electrocatalytic activity toward glycerol oxidation and hydrogen evolution

The catalytic capability of bimetallic nanocatalysts is closely correlated with their size, shape, and crystal structures. Herein, a facile one-pot solvothermal strategy is designed to fabricate uniform spherical PdCu nanocrystals (NCs) assembled by many smaller grains. Oeylamine (OAm) is acted as the reaction solvent and reductant. KBr and hexadecylpyridinium chloride monohydrate (HDPC) are used as the capping agent and surfactant to avoid the aggregation, respectively. The architectures possess larger electrochemically active surface area (ECSA) of 13.6 m² g^?1 than commercial Pd black (4.4 m² g^?1), showing the improved catalytic ability for glycerol oxidation reaction (GOR) in alkaline electrolyte in contrast with Pd black. Besides, the obtained catalyst exhibits more positive onset potential (?56 mV) and Tafel slope (51 mV decade^?1) toward hydrogen evolution reaction (HER) in acidic media relative to commercial Pd/C, albeit with their performance bellow commercial Pt/C catalyst.     

Synthesis of nitrogen-doped MoSe2 nanosheets with enhanced electrocatalytic activity for hydrogen evolution reaction

Benefiting from improved electrical conductivity, the N-doped MoSe₂ nanosheets show substantially enhanced HER activity with a lower onset overpotential of approximately ?135 mV and a smaller Tafel slope of 62 mV dec^?1, which exhibiting enhanced catalytic performance compared with that of pure MoSe₂. The success of improving the HER performance via the introduction of N dopant offers a new opportunity in the development of high performance MoSe₂-based electrocatalyst.     

A high active hydrogen evolution reaction electrocatalyst from ionic liquids-originated cobalt phosphide/carbon nanotubes

Ionic liquid/carbon nanotubes (IL/CNTs) composite was applied as the precursor to prepare CNTs-supported cobalt phosphide via low-temperature phosphidation. CoP_(MBMG)/CNTs, generated from N,N-bis(4-(methoxycarbonyl)benzyl)-N-methyl-d-glucaminium dibromodichlorocobaltate(II) (MBMG)₂-CoCl₂Br₂), exhibits the best catalytic activity toward hydrogen evolution reaction with an onset overpotential of 55 mV, a Tafel slope of 58 mV dec^?1, 95% Faradaic efficiency (FE), current densities of 10 and 20 mA cm^?2 at overpotentials of 135 and 160 mV, and it can maintain the catalytic activity for at least 27 h. FT-IR, Raman spectroscopy, XPS and XRD were utilized to investigate the phosphidation process. All experimental results confirmed that anion from (MBMG)₂-CoCl₂Br₂ can form CoP and glucaminium-based cation can become amorphous carbon after phosphidation to obtain the high HER activity of CoP_(MBMG)/CNTs.     

Cobalt carbonate hydroxide mesostructure with high surface area for enhanced electrocatalytic oxygen evolution

Hydrogen energy utilization from water splitting relies on the successful development of earth-abundant, efficient, and stable electrocatalysts for oxygen evolution reaction (OER). Herein, novel cobalt carbonate hydroxide nanorods are synthesized by facile low-temperature precipitation. The nanorods are networked to form mesoporous structure with a large surface area (291.4 m² g^?1) and high pore volume (1.06 cm³ g^?1). The obtained catalyst reaches a current density of 10 mA cm^?2 with an overpotential of a 320 mV and a Tafel slope of 39 mV dec^?1. Moreover, OER activity is improved after stability test, while the overpotential drops down to 313 mV. This increase in activity is explained by in-situ conversion from carbonate to hydroxide, resulting in an increase of active sites. The synthesis route allows an efficient way for obtaining novel cobalt-based OER electrocatalyst, and the enhancement in catalytic activity after stability test also gives a new insight for designing high-performance OER electrodes.     

Nickel selenide nanostructures as an electrocatalyst for hydrogen evolution reaction

Electrochemical water splitting has gained momentum for the development of alternative energy sources. Herein, we report the synthesis of two different nickel selenide nanostructures of different morphology and composition employing hydrothermal method. NiSe₂ nanosheets were obtained by the anion-exchange reaction of Ni(OH)₂ with Se ions for 15 h. On the other hand, NiSe nanoflakes were synthesized by the direct selenization of nickel surface with the reaction time of 2 h. Tested as an electrocatalyst for hydrogen evolution reaction, NiSe₂ nanosheets and NiSe nanoflakes can afford a geometric current density of 10 mA cm^?2 at an overpotential of 198 mV and 217 mV respectively. The measured Tafel slope values of NiSe nanoflakes are 28.6 mV dec^?1, which is three times lower as compared with NiSe₂ nanosheets (72.1 mV dec^?1). These results indicates the HER kinetics of NiSe nanoflakes are at par with the state-of-the-art Pt/C catalyst and also complimented with the short synthesis time of 2 h. Further, both nickel selenides exhibit ultra-long term stability for 30 h as evident from constant current chronopotentiometry and electrochemical impedance spectroscopy results.     

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.     

Mo incorporated W18O49 nanofibers as robust electrocatalysts for high-efficiency hydrogen evolution

Creation of robust and stable electrocatalysts is a persistent objective for high-efficiency hydrogen evolution by water splitting. We present here the experimental realization of one-dimensional Mo incorporated W₁₈O₄₉ nanofibers (NFs) by a template-free solvothermal method. When utilized as electrocatalysts for hydrogen evolution through water splitting, the preliminary results demonstrate that the optimized catalytic electrode from 1 at% Mo doped W₁₈O₄₉ NFs yields an onset overpotential of 89 mV and Tafel slope of 49 mV dec^?1 as well as maximal exchange current density up to 1.60 × 10^?2 mA cm^?2. An overpotential as low as 462 mV is required to attain current density of 50 mA cm^?2 in comparison with 587 mV for pristine W₁₈O₄₉ NFs. Moreover, the Mo doped W₁₈O₄₉ NFs display relative stability by applying a potential of 503 mV and a current density of 80 mA cm^?2 over 24 h in 0.5 M H₂SO₄ aqueous solution, making them promising in practical applications.     

MOF-directed templating synthesis of hollow nickel-cobalt sulfide with enhanced electrocatalytic activity for oxygen evolution

The development of efficient, universal and cheap electrocatalysts for the utilization in the oxygen evolution reaction (OER) by desired morphology and composition remains a great challenge. Herein, we report a facile and novel method to prepare the porous hollow nickel-cobalt sulfide (NiCoS) by using zeolitic imidazolate framework-67 (ZIF-67) as the template. The obtained NiCoS-3 polyhedron shows superior catalytic activity toward OER with a low overpotential of 320 mV at the current density of 10 mA cm^?2, a small Tafel slope of 58.8 mV dec^?1 and excellent stability. Benefiting from their structural and compositional merits, the as-synthesized NiCoS-3 polyhedron may be a good promising candidate electrocatalysts for water splitting. Present work provides a simple strategy to regulated composition, morphology and catalytic activity relationship, offer an effective way to design a low-cost and efficient electrocatalyst.     

Direct synthesis of nitrogen-rich carbon sheets via polybenzoxazine as highly active electrocatalyst for water splitting

In this work, we propose a novel nitrogen-rich carbon sheets (N-CSs), with conceivable use as efficient catalysts for hydrogen evolution reaction (HER). N-CSs are directly synthesized from polybenzoxazine (PBz) by carbonization followed by KOH activation. PBz was prepared from eugenol, melamine, and paraformaldehyde through ring-opening polymerization. FT-IR and NMR spectroscopy confirmed the corresponding chemical structures of the new benzoxazine monomer. The morphology, structure and surface properties of the N-CSs are investigated by Raman spectroscopy, wide-angle X-ray diffraction, and X-ray photoelectron spectroscopy. The catalytic activity of N-CSs towards HER is thoroughly investigated by electrochemical techniques. In N-CSs, it is established that nitrogen gratified electrocatalytic activity, and hence nitrogen atoms should enhance the electrocatalytic properties by increasing the active sites. As the kinetic current is stabilized by the outer nitrogen atom as such, HER is proposed to proceed on these active sites by the Volmer-Heyrovsky mechanism. The N-CSs show outstanding catalytic activity towards HER with lowest onset-potential (?10 mV_RHE) and Tafel slope (45 mV dec^?1) in 0.5 M H₂SO₄ aqueous electrolyte.     

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.     

Flower-like CoS2/MoS2 nanocomposite with enhanced electrocatalytic activity for hydrogen evolution reaction

Molybdenum sulfide (MoS₂) has received tremendous attracts for its promising performance in the aspects of hydrogen evolution reaction (HER). To improve the HER activity of MoS₂, we designed a flower-shaped CoS₂/MoS₂ nanocomposite with enhanced HER electroactivity compared with MoS₂ nanosheets by a simple one-step hydrothermal method. The facile approach brings about distinct transformation of the morphology from nanosheets to nanoflower structures. The introduction of Co element into MoS₂ results in the larger active surface area, more edge-terminated structures, and higher conductivity of the CoS₂/MoS₂ nanocomposite, which are good for improving the HER electroactivity. In brief, the optimized catalyst exhibits the low overpotential of 154 mV at 10 mA cm^?2, small Tafel slope of 61 mV dec^?1, and excellent stability in acidic solution.     

In-situ grown of Ni2P nanoparticles on 2D black phosphorus as a novel hybrid catalyst for hydrogen evolution

Nickel phosphide-based nanomaterials have been acted as efficient catalysts for the hydrogen evolution reaction (HER), however, the design of novel and high performance HER catalyst is still a challenge. Herein, we report a novel 2D material black phosphorus (BP) as support for constructing Ni₂P-based hybrid catalyst by a one-pot thermal decomposition approach. TEM results indicated that the monodispersed Ni₂P nanoparticles with small size and good dispersion supported on the surface of layered BP, which implied that more catalytic active sites may be exposed for HER. The as-synthesized Ni₂P/BP hybrid exhibits high HER electrocatalytic performance with low onset overpotential (70 mV), small Tafel slope (81 mV dec^?1), large double-layer capacitance (1.24 mF cm^?2), high conductivity and good stability, which can be assigned to the strong synergistic effect between Ni₂P and BP. Therefore, BP may be a suitable support for constructing excellent catalysts in electrocatalysis.     

Co Nanoparticles@N-doped carbon coated on carbon Nanotube@Defective silica as non-noble photocathode for efficient photoelectrochemical hydrogen generation

The development of photoelectrodes capable of light-driven hydrogen evolution from water with non-noble metals is an important approach for the storage of solar energy in the form of a chemical energy carrier. In this study, we report Co nanoparticles@N-doped carbon coated on carbon nanotube@defective-silica (CNTs@Co@NC/D-SiO₂), which are composed of Co nanoparticles@N-doped carbon as electrocatalyst, defective-silica as photocatalyst and carbon nanotube as conductive substrates. The obtained non-noble photocathode possesses the high performance for efficient photoelectrochemical hydrogen evolution reaction. When evaluated for hydrogen evolution reaction electrocatalysis, CNTs@Co@NC/D-SiO₂ exhibits a small onset overpotential of 104 mV (J = 1 mA cm^?2), a Tafel slope of 69.1 mV dec^?1 and outstanding long-term cycling stability. The P type semiconductor characteristics of CNTs@Co@NC/D-SiO₂ due to defective-silica with carrier concentration of 3.53 × 10¹⁹ cm^?3 is measured, which produces a significant positive shift of overpotential of 40 mV (J = 10 mA cm^?2) under 100 mW cm^?2 simulated sunlight irradiation. These findings provide a straightforward and effective route to produce cheap and efficient photo-electro-catalyst for water splitting.     

Hierarchical MoS2 nanoflowers on carbon cloth as an efficient cathode electrode for hydrogen evolution under all pH values

In this paper, a facile hydrothermal synthetic strategy was developed for MoS₂ nanoflowers with enlarged interlayer spacing on the carbon cloth (CC) as a high efficiency cathode electrode for hydrogen evolution reaction (HER) under wide pH condition. It was observed that the loading amount of MoS₂ has a major impact on the HER performance, where the optimized MoS₂/CC exhibited a low onset potential of 94 mV and a small Tafel slope of 50 mV dec^?1 in strong acid solution (pH = 0). The improved HER performance can be contributed to the enlarged interlayer spacing, abundant defects and more exposed active sites in the small size MoS₂ nanosheets as revealed by XRD and HRTEM. Meanwhile, it also exhibited relatively good performance for HER under basic and neutral conditions with the overpotentials of 188 (pH = 14) and 230 (pH = 7) mV to achieve current density of 10 mA cm^?2 and the Tafel slopes of 52 and 84 mV dec^?1, respectively.     

A newly synthesized single crystal zinc complex as molecular electrocatalyst for efficient hydrogen generation from neutral aqueous solutions

A new chlorobis(2-aminomethylbenzimidazole)zinc(II) perchlorate complex [Zn(AMB)₂Cl](ClO₄) 1 has been synthesized and characterized. Spectral and X-ray structural features led to the conclusion that the zinc(II) complex has a square-pyramidal environment around zinc(II) center with coordination chromophore ZnN₄Cl. Different amounts of complex 1 were supported on glassy carbon (GC) electrode yielding three GC-supported complex 1 electrodes with different loading densities (0.2, 0.4, and 0.8 mg cm^?2). These electrodes were tested as molecular electrocatalysts for the hydrogen evolution reaction (HER) in phosphate buffer aqueous solutions (pH 7), employing linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS). Results showed that GC-complex 1 catalysts are highly active for the HER, and this catalytic activity enhances with the loading density. The one with the highest loading density (0.8 mg cm^?2) exhibited high HER catalytic activity with low onset potential of ?140 mV vs. RHE and a high exchange current density of 0.22 mA cm^?2. It required an overpotential of 240 mV to achieve a current density of 10 mA cm^?2. It also recorded a turnover frequency (TOF) of 1722 mol of hydrogen per mole of catalyst per hour at overpotential 500 mV, which is comparable with the most active molecular electrocatalysts reported in the literature for H₂ generation from aqueous neutral solutions. A catalytic cycle is proposed for the generation of hydrogen by complex 1 and the mechanism of the HER is discussed based on the measured Tafel slope (140 mV dec^?1).     

CoSe2 nanoparticles grown on carbon nanofibers derived from bacterial cellulose as an efficient electrocatalyst for hydrogen evolution reaction

Exploration of high-efficiency and inexpensive Pt-free electrochemical catalysts for hydrogen evolution reaction (HER) is highly significative for carbon dioxide free energy conversion systems. In this work, we described the development of CoSe₂ nanoparticles grown on the carbon nanofibers (CNFs) derived from bacterial cellulose (CNFs/CoSe₂) through a facile one-step hydrothermal preparation, which not only showed a three-dimensional (3D) porous network structure, but also possessed large surface area. This rationally designed architecture realizes the uniform distribution of CoSe₂ nanoparticles to provide with fully exposed active edges and the unique conductive interwoven carbon nanofibers facilitates the charge transportation in HER process, thus leading to remarkable HER activity. As expected, the CNFs/CoSe₂ shows a low onset overpotential of ?85 mV, low overpotential (η₁₀ = 119 mV) for reaching a current density of ?10 mA cm^?2 and smaller Tafel slope of 54 mV dec^?1 as well as good cycling stability in acidic electrolyte.     

Large surface and pore structure of mesoporous WS2 and RGO nanosheets with small amount of Pt as a highly efficient electrocatalyst for hydrogen evolution

In this work, mesoporous WS₂ with high surface area was prepared by hard template method. First, a one-step nanocasting generates metal precursor@mesoporous silica SBA-15 composites. A hydrothermal method is subsequently adopted to convert the precursors to sulfides in the confined nanochannels. After etching silica SBA-15, mesoporous layered metal sulfide crystals were obtained as the products. Then, we have put forward a new catalyst based on mesoporous WS_2, RGO nanosheets and Pt nanoparticles as a highly efficient electrocatalyst for hydrogen evolution. The Pt/WG-2 nanostructure electrocatalyst in this report exhibits excellent performance with a small Tafel slope of 47 mV dec^?1, long-term durability and an overpotential of 95 mV in 0.5 M H₂SO₄ for the hydrogen evolution reaction (HER).     

Defect-rich MoSx/carbon nanofiber arrays on carbon cloth for highly efficient electrocatalytic hydrogen evolution

Engineering MoS₂ catalysts with more active sites and higher conductivity is an effective way to improve its electrochemical activity. Herein, defect-rich amorphous MoS_x/carbon nanofiber (CF) arrays on carbon cloth (CC) support (denoted as MoS_x/CF/CC) was designed and fabricated, which served as an efficient free-standing electrocatalyst for hydrogen evolution reaction (HER) in acid media. This architecture was beneficial to expose more active catalytic sites and improve the electron/ion transport. In addition, abundant defects altered preferred growth direction of MoS_x, resulting in the formation of irregular MoS_x particles at the surface of CF arrays. The as-synthesized MoS_x/CF/CC-2 exhibited excellent stability and superior HER activity, with a small onset overpotential (107 mV) and low Tafel slope (51 mV dec^?1). Such excellent electrochemical performance was attributed to the enriched active sites and shortened charge diffusion distance. This work would pave a new way for rational design and fabrication of defect-rich MoS_x-based composite electrode for renewable energy applications.