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.     

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.     

One-step synthesis of amorphous Ni–Fe–P alloy as bifunctional electrocatalyst for overall water splitting in alkaline medium

Design of inexpensive and highly efficient bifunctional electrocatalyst is paramount for overall water splitting. In this study, amorphous Ni–Fe–P alloy was successfully synthesized by one-step direct-current electrodeposition method. The performance of Ni–Fe–P alloy as a bifunctional electrocatalyst toward both hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) was evaluated in 30 wt% KOH solution. It was found that Ni–Fe–P alloy exhibits excellent HER and OER performances, which delivers a current density of 10 mA cm^?2 at overpotential of ～335 mV for HER and ～309 mV for OER with Tafel slopes of 63.7 and 79.4 mV dec^?1, respectively. Moreover, the electrolyzer only needs a cell voltage of ～1.62 V to achieve 10 mA cm^?2 for overall water splitting. The excellent electrocatalytic performance of Ni–Fe–P alloy is attributed to its electrochemically active constituents, amorphous structure, and the conductive Cu Foil.     

Preparation and evaluation of a new hybrid support based on exfoliation of graphite by ball milling for Ni nanoparticles in hydrogen evolution reaction

A mixture of graphene/graphite as new support was prepared by ball milling procedure and was used for Nickel nanoparticles supported that was employed as a cathode catalyst for hydrogen evolution reaction (HER) in the KOH solution. The structure and electrocatalytic activity of electrocatalyst were investigated by Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD) analysis, and electrochemical techniques. The results indicated that by raising the time of the ball milling from 0 to 270 min, the HER activity of electrocatalyst first increased, and then decreased according to the increase of active sites and then agglomeration of Ni nanoparticles. Ni nanoparticles supported on the mixture with 180 min ball milling exhibited the highest HER activity with a low overpotential (205 mV at 10 mA cm^?2), Tafel slope of 84 mV dec^?1, and remarkable durability.     

Ni/NiO@rGO as an efficient bifunctional electrocatalyst for enhanced overall water splitting reactions

Herein, we fabricated bifunctional, noble metal-free, highly efficient nickel/nickel oxide on reduced graphene oxide (Ni/NiO@rGO) by chemical synthesis approach for electrochemical water splitting reaction. Its structural and morphological characterization using thermogravimetric analysis (TGA), transmission electron microscopy (TEM), field emission scanning electron microscope (FESEM), energy dispersive analysis of X-ray (EDAX) and X-ray diffraction (XRD) represents, Ni/NiO@rGO is having Ni/NiO NPs ∼10 nm (±2 nm) on graphene oxide with face-centered cubic (FCC) crystal structure. Moreover, the presence of Ni/NiO (2.26%), O (6.56%), N (0.74%) and C (90.44%) from EDAX analysis further confirms the formation of Ni/NiO@rGO and it also supported by FTIR studies. This nanocatalyst is examined further for electrocatalytic water splitting reactions (HER and OER). It demonstrated low overpotential 582 mV to achieve current density at 10 mA cm⁻² and smaller Tafel slope of 63 mV dec⁻¹ obtained in 0.5 M H₂SO₄ towards HER. Also, at the other end at onset potential of 1.6 V vs. RHE towards OER. It demonstrated low overpotential 480 mV to achieve current density at 10 mA cm⁻² and smaller Tafel slope of 41 mV dec⁻¹ in 0.5 M KOH towards OER observed. Hydrogen fuel is eco-friendly to the environment and noteworthy performance of earth-saving reactions.     

Co/VN heterostructure coated with holey interconnected carbon frameworks as bifunctional catalysts

The development of transition-metal electrocatalyst is of great importance to bring down costs and enhance performance for fuel cells and water splitting. The multiple efforts have been concentrated on bifunctional electrocatalysts toward hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR). Only a few works reach desirable durability and performance levels. Here, Co/VN heterostructure with rational porous structure is formed in response to the sensible cobalt and vanadium ratio. Owing to synergistic interaction of holey interconnected structure with large surface area of 57 m² g^?1 and abundant interfaces between Co and VN phases, Co/VN@NC presents superior bifunctional electrocatalytic performance towards both HER and ORR. Co/VN@NC drives the reaction with low overpotential η₁₀ of 96 mV and Tafel slope of 82 mV dec^?1 along with outstanding stability for HER. Furthermore, Co/VN@NC obtains an onset potential (0.954 V) and half-wave potential (0.796 V) with superior methanol tolerance and durability for ORR.     

Porous NiFe alloys synthesized via freeze casting as bifunctional electrocatalysts for oxygen and hydrogen evolution reaction

Binder-free NiFe-based electrocatalyst with aligned pore channels has been prepared by freeze casting and served as a bifunctional catalytic electrode for oxygen and hydrogen evolution reaction (OER and HER). The synergistic effects between Ni and Fe result in the high electrocatalytic performance of porous NiFe electrodes. In 1.0 M KOH, porous Ni₇Fe₃ attains 100 mA cm⁻² at an overpotential of 388 mV with a Tafel slope of 35.8 mV dec⁻¹ for OER, and porous Ni₉Fe₁ exhibits a low overpotential of 347 mV at 100 mA cm⁻² with a Tafel slope of 121.0 mV dec⁻¹ for HER. The Ni₉Fe₁//Ni₉Fe₁ requires a low cell voltage of 1.69 V to deliver 10 mA cm⁻² current density for overall water splitting. The excellent durability at a high current density of porous NiFe electrodes has been confirmed during OER, HER and overall water splitting. The fine electrocatalytic performances of the porous NiFe-based electrodes owing to the three-dimensionally well-connected scaffolds, aligned pore channels, and bimetallic synergy, offering excellent charge/ion transfer efficiency and sizeable active surface area. Freeze casting can be applied to design and synthesize various three-dimensionally porous non-precious metal-based electrocatalysts with controllable multiphase for energy conversion and storage.     

Electrochemical synthesis of Li-doped NiFeCo oxides for efficient catalysis of the oxygen evolution reaction in an alkaline environment

Oxygen evolution reaction (OER) is an essential reaction for overall electrochemical water splitting. In this present study, we adopt a facile electrochemical deposition method to synthesize the Li-doped NiFeCo oxides for OER in an alkaline medium. The scanning electron microscopy, X-ray diffraction, Brunauer-Emmet-Teller method and X-ray photo-electron spectroscopy provides the information of morphology, structure, specific surface area and electronic state of the electrocatalysts respectively. Investigates the electrochemical properties by the thin-film technique on a rotating disk electrode and in a single-cell laboratory water electrolyzer connects with electrochemical impedance spectroscopy. Among the catalysts under investigation, Ni_0·9Fe_0·1Co_1·975Li_0·025O₄ exhibits the highest activity towards oxygen evolution reaction, and explains the activity by the oxygen binding energy; such knowledge can be helped to develop better catalyst. We achieve onset over potential 220 mV and receive 10 mA cm^?2 current density at over potential 301 mV with Tafel slope 62 mV dec^?1 in 1 M KOH solution. The results are similar to recently published catalysts in the literature. In water electrolyzer, the Ni_0·9Fe_0·1Co_1·975Li_0·025O₄ modified nickel foam anode exhibits a current density of 143 mA cm^?2 at a cell voltage of 1.85 V in 10 wt% KOH and a temperature of 50 °C.     

Green synthesized N-doped graphitic carbon sheets coated carbon cloth as efficient metal free electrocatalyst for hydrogen evolution reaction

Heteroatom doped carbon structures received a great attention owing to its applications in catalysis, energy and optics. In this work, a simple hydrothermal approach for the synthesis of nitrogen doped graphitic carbon sheets (N-GCSs) is reported. Rubus parvifolius (R. parvifolius) fruit juice and aqueous ammonia are used as carbon precursor and nitrogen dopant, respectively. The synthesized N-GCSs are characterized using Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Raman spectroscopy, high resolution transmission electron microscopy (HR-TEM) and field emission scanning electron microscopy (FE-SEM) coupled with energy dispersive spectrum (EDS). The presence of hydroxyl and carbonyl functionalities in the synthesized N-GCSs are confirmed by the FT-IR analysis. The doping of nitrogen in N-GCSs is revealed through the XPS spectrum. The XRD and Raman studies imply that the synthesized N-GCSs are moderate graphitic nature. The FE-SEM and HR-TEM images of N-GCSs exposed its sheet like porous morphology. The electrocatalytic activity of N-GCSs coated carbon cloth (N-GCSs/CC) are examined towards hydrogen evolution reaction (HER) in 0.50 M H₂SO₄ using linear sweep voltammetry (LSV), Tafel and electrochemical impedance spectroscopy (EIS) studies. The onset potential of synthesized N-GCSs/CC is about ?0.25 V_RHE, which is lower than that of bare carbon cloth (CC) ?0.75 V_RHE. The Tafel slope of N-GCSs/CC is smaller (198 mV dec^?1) than that of bare CC (253 mV dec^?1), suggested fast kinetics of N-GCSs. Moreover, the N-GCSs/CC is attained ?10 mA cm^?2 of current density at very low over potential of ?0.320 V_RHE. The EIS studies also proved the excellent catalytic activity of N-GCSs/CC towards HER. Thus, the R. parvifolius derived N-GCSs is a better candidate for HER in acidic medium.     

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.     

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.     

Porous CoP nanostructure electrocatalyst derived from DUT-58 for hydrogen evolution reaction

The development of efficient, non-precious metal catalysts for preparing hydrogen by water decomposition, which is a perfect alternative for increasingly serious environmental pollution and energy needs. In this work, we report that a porous CoP-350 nanostructure material was prepared using Co-based metal organic frameworks (DUT-58) as the precursor by pyrolysis and low temperature phosphating. The porous CoP-350 nanostructure electrocatalyst in this report exhibits excellent performance with a small Tafel slope of 64 mV dec^?1, long-term durability and an overpotential of 126 mV at current density 10 mA cm^?2 in 0.5 M H₂SO₄ for the hydrogen evolution reaction (HER). All in all, this work provides an approach to synthesize porous CoP nanostructure as the transition metal phosphides catalyst.     

Constructing Ni-Modified Co-FcDA nanosheets for enhancing electrocatalytic oxygen evolution reaction

Electrocatalytic water splitting is an emerging technology for the development of maintainable hydrogen energy. It remains challenging to manufacture a stable, efficient, and cost-effective electrocatalyst that can conquer the slow reaction kinetics of water electrolysis. Herein, A metal-organic framework (MOF) based material is manufactured and productively catalyze the oxygen evolution reaction (OER). The introduction of elemental nickel enhances the catalytic activity of Co-FcDA. The results show that single Ni was well doped in the CoNi-FcDA catalysts and the doping of Ni has a great influence on the OER activity of CoNi-FcDA catalysts. CoNi-FcDA displayed a low overpotential of 241 mV to arrive at the benchmark current density (10 mA cm^?2) with a remarkably small Tafel slope of 78.63 mV dec^?1. It surpassed the state-of-the-art electrocatalyst for OER, that is, RuO₂ (260 mV and 97.26 mV dec^?1) in efficiency as well as instability. Density functional theory (DFT) calculations show that suitable Ni doping at the same time can increase the density of states of the Fermi level, resulting in excellent charge density and low intermediate adsorption energy. These discoveries provide a practical route for designing 2D polymetallic nanosheets to optimize catalytic OER performance.     

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.     

Efficient and stable HER electrocatalyst using Pt-nanoparticles@poly(3,4–ethylene dioxythiophene) modified sulfonated graphene nanocomposite

The green production of hydrogen by electrochemical water splitting has been recently paid attention. It is more focused to research about the preparation of efficient electrocatalysts, which catalyze hydrogen evolution reaction (HER) in acidic media at low overpotential. Platinum is known as an ideal option, but its rarity and high-cost limit its application in practical industrial plants. Hence, minimizing the level of it can be a solution. It can be achieved by the decoration of platinum nanoparticles (PtNPs) on the different composites such as poly(3,4–ethylene dioxythiophene, PEDOT) and sulfonated graphene nanosheets (SG) in this work. Accordingly, the successful preparation and HER electrocatalytic manner of this nanocomposite were main objectives in the present report. The related characterization and performance were monitored using various analytical and electrochemical techniques. The low charge transfer resistance (around 50 Ω), low overpotential (?0.040 V vs. RHE), and stable manner (until 500 cycles) resulted in this HER electrocatalyst. It was controlled by Tafel reaction with electrochemical adsorption-desorption because of kinetic factors including Tafel slope (28.4 mV dec^?1), charge-transfer coefficient of 2.0, and exchange current of 7.27 mA cm^?2.     

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.     

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).     

Cytosine assisted aqueous synthesis of AgPt hollow alloyed nanostructures as highly active electrocatalyst for ethylene glycol oxidation and hydrogen evolution

Herein, a simple one-pot aqueous method was developed for synthesis of AgPt hollow alloyed nanostructures (AgPt HANS) with polyvinylpyrrolidone (PVP) and cytosine as the dispersing agent and eco-friendly growth-director, respectively. The synthesized architectures displayed the improved catalytic performance toward ethylene glycol oxidation reaction (EGOR) relative to commercial Pt black in alkaline media. Meanwhile, the catalyst exhibited the enhanced catalytic activity for hydrogen evolution reaction (HER) with the positive onset potential (E_onset, ?39 mV) and a small Tafel slope (40 mV dec^?1) relative to commercial Pt/C (20 wt%, ?31 mV, 33 mV dec^?1) in 0.5 M H₂SO₄, along with the more positive E_onset (?34 mV) and a smaller Tafel slope (59 mV dec^?1) in 0.5 M KOH compared with Pt/C (?35 mV, 85 mV dec^?1).     

Novel 13X Zeolite/PANI electrocatalyst for hydrogen and oxygen evolution reaction

In this work, first 13X zeolite was prepared by the hydrothermal method. Then, the composite electrode was fabricated by using 13X zeolite and aniline monomer in nickel foam by electropolymerization technique in an acidic medium (13X/PANI). The synthesized 13X zeolite was characterized by physicochemical characterization techniques such as Fourier transform infra-red (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD) pattern and nitrogen sorption isotherm. 13X/PANI composite was further analyzed by XRD, XPS and FE-SEM techniques. Furthermore, the catalyst activity of the synthesized 13X, PANI and 13X/PANI composite electrodes was evaluated in hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) by using linear square voltammetry (LSV) and Tafel slope method. The Tafel slopes of HER were found to be 203 mV dec⁻¹, 440 mV dec⁻¹ and 282 mV dec⁻¹ for 13X, PANI and 13X/PANI-15 electrodes respectively. While the OER Tafel slopes were found to be 423 mV dec⁻¹, 310 mV dec⁻¹ and 168 mV dec⁻¹ for 13X, PANI and 13X/PANI-15, respectively. 13X/PANI-15 electrodes show excellent catalytic performance about the overpotential at 10 mA cm⁻² for HER and the overpotential at 20 mA cm⁻² for OER. The obtained results suggest fabricated novel electrodes are a potential candidate for HER and OER reaction and can be open new avenue for other electrochemical reactions.     

One-step synthesis of the 3D flower-like heterostructure MoS2/CuS nanohybrid for electrocatalytic hydrogen evolution

In this work, a facile one-step hydrothermal method was developed to fabricate three types different of nanomaterials: the two-dimension (2D) of MoS₂ nanosheets; 3D spherical CuS nanoparticles; and 3D flower-like heterostructure of MoS₂/CuS nanohybrid, respectively. The as-synthesized MoS₂, CuS and MoS₂/CuS were characterized by transmission electron microscopy (TEM), field emission scanning electron microscopy (SEM) and X-ray diffraction (XRD) etc. The morphology of the MoS₂/CuS nanohybrid is different from the MoS₂ nanosheets and CuS nanoparticles. The hydrogen evolution reaction (HER) activity of MoS₂ nanosheets, CuS nanoparticles and MoS₂/CuS nanohybrid, were investigated by the Linear Sweep Voltammetry (LSV) and Tafel slope. The HER activity of MoS₂/CuS nanohybrid is better than those of MoS₂ nanosheets and CuS nanoparticles, which can be attributed to the good electron-transport ability of CuS and the strong reduction ability of hydrogen ions by MoS₂. Thus, MoS₂/CuS nanohybrid exhibited excellent activity for HER with a small onset potential of 0.15 V, a low Tafel slope of 63 mV dec^?1, and relatively good stability. However, the MoS₂ nanosheets and CuS nanoparticles respectively shows a bigger onset potential of 0.25 V and 0.35 V, a higher Tafel slope of 165 and 185 mV dec^?1. This 3D flower-like heterostructure of MoS₂/CuS nanohybrid catalyst exhibits great potential for renewable energy applications.