Facile synthesis of MoS2/N-doped macro-mesoporous carbon hybrid as efficient electrocatalyst for hydrogen evolution reaction

A novel three-dimensional (3D) hybrid consisting of molybdenum disulfide nanosheets (MoS₂) uniformly bound at N-doped macro-mesoporous carbon (N-MMC) surface was fabricated by the solvothermal method. The resulting MoS₂/N-MMC hybrid possesses few-layer MoS₂ nanosheets structure with abundant edges of MoS₂ exposed as active sites for hydrogen evolution reaction (HER), in sharp contrast to large aggregated MoS₂ nanoflowers without N-MMC. The high electric conductivity of N-MMC and an abundance of exposed edges on the MoS₂ nanosheets make the hybrid excellent electrocatalytic performance with a low onset potential of 98 mV, a small Tafel slope of 52 mV/decade, and a current density of 10 mA cm^?2 at the overpotential of 150 mV. Moreover, the MoS₂/N-MMC hybrid exhibits outstanding electrochemical stability and structural integrity owing to the strong bonding between MoS₂ nanosheets and N-MMC.     

Coupling molybdenum carbide nanoparticles with N-doped carbon nanosheets as a high-efficiency electrocatalyst for hydrogen evolution reaction

Searching for earth-abundant and high-efficiency electrocatalysts for the hydrogen evolution reaction (HER) is of critical importance for future energy conversion devices. To facilitate the HER on a nonprecious metal-based catalyst, integration of catalytically active nanoparticles with highly conductive carbon supports represents a promising strategy since the formed nanohybrid can offer available active sites and improved electron transfer capability. Herein, we demonstrate a feasible and scalable approach to fabricate well-dispersed Mo₂C nanoparticles firmly anchored on 2D ultrathin N-doped carbon nanosheets (denoted as Mo₂C@NC nanosheets) using inexpensive NaCl as recyclable templates. The adoption of NaCl template provides a 2D space for the one-step concurrent growth of Mo₂C nanoparticles and N-doped carbon nanosheets. Benefiting from the synergy between fine Mo₂C nanoparticles with high dispersity and N-doped C nanosheets, the resultant Mo₂C@NC nanosheets exhibit an outstanding HER performance with a low overpotential, a small Tafel slope and excellent stability under acidic medium, making them a promising noble-metal-free HER catalyst.     

Synthesis and characterization of Ni-Mo2C particles supported over hydroxyapatite for potential application as a catalyst for hydrogen production

Ni-Mo₂C particles supported over hydroxyapatite were synthesized as potential catalysts to hydrogen production applications due their physiochemical properties observed in characterization results, this favorable for biomass gasification. Mo₂C particles doped with Ni were synthesized by temperature programmed reaction method at 900 °C under hydrogen reducing atmosphere. Hydroxyapatite support was obtained from thermal extraction of bovine bones, in a temperature range from 700 to 900 °C. Ni-Mo₂C impregnation over hydroxyapatite support was made by incipient humidity method. X-ray diffraction analysis determined crystallographic phases of β-Mo₂C, NiC and hydroxyapatite. Though, bone organic matter degradation was observed by X-ray diffraction and confirmed by Infrared Spectroscopy with Fourier Transform (FTIR) the final structure of hydroxyapatite was maintained. Finally, textural properties analysis of support showed an increase in porosity structure with the increment of temperature. β-Mo₂C and NiC were obtained with similar catalytic activity than noble metals, also nickel improves hydrocarbons bonds rupture. Hydroxyapatite showed high stability and porosity at elevated temperatures attributable to synthesis conditions.     

Facile one-step synthesis of nitrogen-doped carbon sheets supported tungsten carbide nanoparticles electrocatalyst for hydrogen evolution reaction

Exploring non-precious metal catalysts with high activity and stability to replace Pt-based materials is vital for electrochemical water splitting. In this work, a facile one-step method was put forward to synthesize WC/NC composite. Due to the couple effect of KCl/NaCl salt and dicyandiamide, pure WC phase was obtained at 900 °C. Meanwhile, KCl/NaCl salt eliminated the runaway pyrolysis expansion of glucose. Besides contributing to the special surface area, dicyandiamide as N source significantly alleviated W mass loss trigged by KCl/NaCl salt and ensured the appropriate WC content in WC/NC composite. As a HER electrocatalyst in acid media, WC/NC composite exhibits the small overpotential of 156 mV at a current density of 10 mA cm⁻², the low Tafel slope of 64 mV dec⁻¹, as well as the robust stability. This work offers a feasible option to fabricate low-cost and effective transition metal carbide electrocatalysts on a large-scale for hydrogen evolution reaction.     

Pt-WC/C as a cathode electrocatalyst for hydrogen production by methanol electrolysis

A novel tungsten carbide promoted Pt/C (Pt-WC/C) was prepared by an intermittent microwave heating (IMH) method and used for the cathode electrocatalyst in an electrolyser for hydrogen production by methanol electrolysis. The electrolyser showed better performance for hydrogen production using the Pt-WC/C cathode electrocatalyst than using a commercial Pt/C cathode electrocatalyst. The single cell electrolyser gave reasonable current at voltages lower than 0.4 V. The novelty of this technique is the inherent simplicity and substantially lowered cost.     

Hydrogen evolution reaction of low carbon steel electrode in hydrochloric acid as a source for hydrogen production

The hydrogen evolution reaction (HER) (cathodic reaction) of low carbon steel electrode immersed in hydrochloric acid was investigated as a source for hydrogen production. Corrosion rate, hydrogen evolution rate, and current density increase with the increase of HCl concentration. Theoretically and practically, every 1 g of iron produces about 0.036 g of hydrogen. Therefore, the hydrogen production efficiency over the immersion period is about 100%. High correlation coefficient (close to +1) statistically indicates that there is a strong relation between loss in weight and the amount of evolved hydrogen (as dependent variable) and both time of immersion and acid concentrations (as independent variables). Application of the hydrogen produced by low carbon steel electrode has been performed on storage material. The tested material absorbs about 6 wt.% of hydrogen under atmospheric pressure and room temperature.     

Hierarchical molybdenum carbide/N-doped carbon as efficient electrocatalyst for hydrogen evolution reaction in alkaline solution

Development of highly-active and noble-metal-free electrocatalysts for hydrogen evolution reaction (HER) is of critical challenge for water splitting, and optimizing the structure and the composition of the relative materials is very necessary to obtain the high-quality catalysts. Herein, a novel molybdenum carbide/N-doped carbon (Mo₂C/NC) hybrid is fabricated by using the hierarchical polyaniline tube network as a carbon source and a reactive template, and the as-fabricated Mo₂C/NC hybrid possesses a uniform hierarchical tube structure. The coupling of the ultrafine Mo₂C nanoparticles and the N-doped carbon substrate provides the abundant active sites and accelerates the charge transfer process. The final Mo₂C/NC catalyst gives the excellent catalytic activity for HER in alkaline condition, which shows a lower overpotential of 142 mV at 10 mA cm^?2 and a small Tafel slope of 61 mV decade^?1 in 1 M KOH.     

Mo2C regulated by cobalt components doping in N-doped hollow carbon nanofibers as an efficient electrocatalyst for hydrogen evolution reaction

Hydrogen is a viable substitute to fossil fuels and electrochemically catalyzed hydrogen evolution has attracted wide attention due to its stability and effectiveness. Nevertheless it is still a major challenge to design and prepare highly active noble metal-free electrocatalysts with controllable structure and composition for efficient hydrogen evolution reaction (HER). Herein, Mo₂C regulated by cobalt components (Co and CoO) doping in N-doped hollow carbon nanofibers (marked as Mo₂C/Co/CoO-NHCNFs) are firstly designed and prepared via a facile coaxial electrospinning followed by calcination process. The one-dimensional conductive carbon host, hollow structure and synergistic effect among CoO, Co and Mo₂C can jointly promote electron transfer, augment exposure of active sites and adjust the electronic structure of the active sites, resulting in the excellent of HER performances. The optimized catalyst has a high specific surface area of 101.27 m² g^?1. Meanwhile, it has a low overpotential of 143 mV at a current density of 10 mA cm^?2 and a small Tafel slope of 74 mV dec^?1 in 1.0 M KOH.Satisfactorily, the overpotential is reduced by 231 mV at the same current density compared with Mo₂C doped in N-doped carbon nanofibers (named as Mo₂C-NCNFs). Moreover, the Mo₂C/Co/CoO-NHCNFs also demonstrate superior long-term stability. The formative mechanism of Mo₂C/Co/CoO-NHCNFs is expounded, and the construction technique is established. The design philosophy and the simple and economical method are of significance for development of HER electrocatalysts.     

Facile synthesis of electrospun C@NiO/Ni nanofibers as an electrocatalyst for hydrogen evolution reaction

Hydrogen evolution reaction (HER) is considered to be one of the most important electrochemical reactions from both fundamental and application perspective to produce hydrogen. Polyacrylonitrile (PAN) based carbon (C)@NiO/Ni nanofibers were fabricated via simple electrospinning method. The as-prepared C@NiO/Ni nanofibers were characterized by scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), scanning electron microscopy Energy Dispersive X-ray Spectroscopy (SEM-EDS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and Raman spectra. The SEM and TEM analyses revealed that NiO/Ni nanoparticles distributed on the PAN based carbon nanofibers. EDS, XPS and XRD results confirm the presence of the nanoparticles. The catalytic activity and durability of C@NiO/Ni nanofibers containing different weight ratio of Ni salt content (2%, 3%, & 4%) were examined for HER in 1 M KOH solution. It has been observed that C@NiO/Ni nanofibers containing Ni content (4%) showed the highest catalytic activity. It indicates that the catalytic activity of electrocatalyst can be enhanced by increasing the effective active sites. Noteworthy to mention here that the nanofibers catalyst reached a current density of 60 mA/cm². The as-prepared catalyst showed remarkable stability up to 22 h and retained 99% of its initial activity even after 16 h of reaction.     

Catalysts evaluation for production of hydrogen gas and carbon nanotubes from the pyrolysis-catalysis of waste tyres

Six different types of catalysts (nickel, iron, and cobalt each supported by γ-Al₂O₃ and activated carbon) that were prepared via impregnation were used to produce hydrogen (H₂) and carbon nanotubes (CNTs) from the pyrolytic product of waste tyres. A two-stage pyrolytic-catalytic reactor was constructed, in which the waste tyre was pyrolyzed in the first pyrolysis reactor, and the resultant pyrolysis vapors underwent the reforming and upgrading step in the downstream catalytic reactor. The results showed that the interaction between the active metal and its support had a remarkable effect on the production of H₂ and CNTs. Compared with the series of γ-Al₂O₃ supported catalysts, all the activated carbon-supported catalysts showed higher H₂ yields and better CNTs quality. For the same catalyst support (γ-Al₂O₃ or activated carbon), the higher yield of H₂ and better quality of CNTs were obtained by the Ni catalysts, followed by the Fe catalysts and the Co catalysts. Among all the catalysts, Ni supported by activated carbon exhibited the best catalytic performance, producing the highest hydrogen yield (59.55 vol.%) and the best CNT quality. Further investigation about the influence of CH₄ and naphthalene as the carbon source on generated CNTs revealed that CH₄ led to longer CNT length and higher graphitization than naphthalene.     

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.     

Facile synthesis of tubular CoP as a high efficient electrocatalyst for pH-universal hydrogen evolution

A facile three-step approach for tubular CoP preparation and its catalytic activity for HER and OER are reported. The CoP microtubes show superior HER performance in a wide pH range with low overpotentials of 91, 101 and 113 mV at 10 mA cm^?2 in 0.5 M H₂SO₄, 1 M KOH and 1 M PBS, respectively. Additionally, it also depicts superior OER performance with an overpotential of 300 mV at 10 mA cm^?2, which is lower than reported precious metal oxides. The improved electrocatalytic performance of tubular CoP is likely attributed to the porous tube-like structural features, which not only afford rich exposed active sites, but also accelerate the charge or mass transfer efficiency, and thus efficiently promote the HER performance. The synthesis of tubular CoP confirms the importance of morphology features and provides a new insight to rationally design and synthesize highly effective non-noble metal phosphide-based pH-universal electrocatalysts for HER.     

Facile fabrication of nickel/porous g-C3N4 by using carbon dot as template for enhanced photocatalytic hydrogen production

Ni/porous g-C₃N₄ was prepared by high temperature thermal polymerization process using carbon dots as soft template and photodeposition. With nickel nanoparticles supported as co-catalyst, the hydrogen evolution reaction (HER) activity of the photocatalyst has been significantly enhanced under visible light, which is up to 1273.58 μmol g⁻¹ h⁻¹, superior to pristine g-C₃N₄ (4.12 μmol g⁻¹ h⁻¹). This is attributed to the inhibited recombination of photogenerated electron-hole pairs and the much better electron transport efficiency. The formed porous structure of carbon nitride could facilitate light utilization and together with nickel nanoparticles, better charge separation can be realized which are proved by the photoluminescence, time-resolved photoluminescence spectra, transient photocurrent measurements and electrochemical impendence spectroscopy. This work provides a useful route to obtain less expensive and efficient photocatalyst containing no noble metals for hydrogen production.     

Techno-economic feasibility assessment of sorption enhanced gasification of municipal solid waste for hydrogen production

Waste-to-fuel coupled with carbon capture and storage is forecasted to be an effective way to mitigate the greenhouse gas emissions, reduce the waste sent to landfill and, simultaneously, reduce the dependence of fossil fuels. This study evaluated the techno-economic feasibility of sorption enhanced gasification, which involves in-situ CO₂ capture, and benchmarked it with the conventional steam gasification of municipal solid waste for H₂ production. The impact of a gate fee and tax levied on the fossil CO₂ emissions in economic feasibility was assessed. The results showed that the hydrogen production was enhanced in sorption enhanced gasification, that achieved an optimum H₂ production efficiency of 48.7% (T = 650 °C and SBR = 1.8). This was 1.0% points higher than that of the conventional steam gasification (T = 900 °C and SBR = 1.2). However, the total efficiency, which accounts for H₂ production and net power output, for sorption enhanced gasification was estimated to be 49.3% (T = 650 °C and SBR = 1.8). This was 4.4% points lower than the figure estimated for the conventional gasification (T = 900 °C and SBR = 1.2). The economic performance assessment showed that the sorption enhanced gasification will result in a significantly higher levelised cost of hydrogen (5.0 €/kg) compared to that estimated for conventional steam gasification (2.7 €/kg). The levelised cost of hydrogen can be reduced to 4.5 €/kg on an introduction of the gate fee of 40.0 €/t_MSW. The cost of CO₂ avoided was estimated to be 114.9 €/tCO₂ (no gate fee and tax levied). However, this value can be reduced to 90.1 €/tCO₂ with the introduction of an emission allowance price of 39.6 €/tCO₂. Despite better environmental performance, the capital cost of sorption enhanced gasification needs to be reduced for this technology to become competitive with mature gasification technologies.     

Decomposition of hydrogen iodide via wood-based activated carbon catalysts for hydrogen production

In this study, the catalytic activity of wood-based catalysts produced by different activation methods was evaluated for the decomposition of hydrogen iodide (HI) as part of the sulfur-iodine hydrogen production process. The wood-based activated carbon catalysts showed strong improvement in the HI conversion compared to a blank, especially for carbon catalysts activated using H₃PO₄. Proximate analysis and ultimate analysis, XRD, BET, SEM, Boehm titration, TPD-MS, XPS were carried out to examine the characteristics of the catalysts. High carbon content (C_ad) seemed to favor high catalytic activity, while high ash content (A_ad) reduced catalytic activity of samples likely due to displacement of catalytically active material. Oxygen-containing groups were not directly responsible for catalytic activity. HI conversion increased as the surface area and pore diameter increased. Unsaturated carbon atoms maybe the main active constituent, therefore, low area density of oxygen [O] that was closely related to unsaturated carbon atoms was beneficial to HI conversion.     

Molybdenum disulfide decorated palm oil waste activated carbon as an efficient catalyst for hydrogen generation by sodium borohydride hydrolysis

Development of cost-effective catalyst material with enhanced activity for hydrogen generation is highly desirable for hydrogen powered portable applications. In this work, molybdenum disulfide (MoS₂) incorporated on palm oil waste activated carbon (POAC) was used as a novel catalyst for enhanced hydrogen production by sodium borohydride (NaBH₄) hydrolysis. Hydrothermally synthesized MoS₂/POAC catalyst composite was characterized by SEM, EDX, XRD, FTIR, Raman, TGA and Surface area analysis. Characterization studies revealed the uniform and complete synthesis of MoS₂ nanoparticles on the POAC surface with crystallite size of 18.2 nm. The catalyst composite showed enhancement in thermal stability and reduction in specific surface area as compared with POAC. Hydrogen generation investigations showed ideal weight ratio of composite catalyst as 10:1 (w/w of POAC: MoS₂) and optimal catalyst to feed weight ratio as 0.07. MoS₂/POAC catalyst with 10 wt% of POAC loading recorded the maximum catalytic activity of 1170.66 mL/g min with lower activation energy of 39.1 kJ/mol. The catalyst composite exhibited virtuous reusability with a 28% loss in activity for nine cycle regeneration run. Thus, MoS₂/POAC catalyst system is highly attractive for commercial applicability and is a potential candidate for enhanced hydrogen production through NaBH₄ hydrolysis.     

Facile synthesis of self-supported intertwined columnar NiCoP as a high efficient electrocatalyst for hydrogen evolution reaction

A new self-supported nickel-cobalt phosphide (NiCoP) on Ni foam (NiCoP/NF) is fabricated by simple immersion in Co(NO₃)₂ solution followed by subsequent phosphorization. NiCoP/NF displays intertwined and porous columnar morphology derived from topological transformation of corresponding columnar amorphous hydroxides precursor. NiCoP/NF manifests the most prominent hydrogen evolution reaction (HER) performance in both 0.5 M H₂SO₄ and 1 M KOH with the overpotentials of 49 and 57 mV to achieve 10 mA cm^?2, respectively. Also, NiCoP/NF showed excellent oxygen evolution reaction (OER) performance, requiring 256 mV to achieve 10 mA cm^?2, even superior to that of RuO₂ and IrO₂. Such impressive HER performance of NiCoP/NF is mainly attributed to the collective effects of enlarged surface area and enriched exposed active sites, affording faster charge transfer kinetic in HER process. This simple immersion method offers a new insight to design cost-effective and efficient electrocatalysts for large scale application.     

Comparative assessment of various gasification fuels with waste tires for hydrogen production

In this paper, waste tires are comparatively studied and assessed as a feedstock relative to coal and coconut char. An Integrated Gasification Combined Cycle (IGCC) is developed by using the Aspen Plus to assess the suggested gasification feedstocks based on their carbon dioxide emissions and hydrogen production to feed rate ratios. Note that many tires are disposed of every year in North America and are stockpiled in the masses in landfills, which cause various environmental implications. In the present study, it is found that waste tires as a feedstock for gasification are a viable solution to this ever-rising problem. The hydrogen production to feed rate ratio is found to be 0.158 which is very competitive with high-quality coals and coconut char. The net power production from the combined cycle when tires are used as the feedstock for the gasifier is found to be 11.1kW. The optimal hydrogen production to feed rate ratio is also achieved at the maximum net power production rate. The energy and exergy efficiencies of the overall system are found to be 55.01% and 52.31% when the waste tires are used as a feedstock.     

Areca leaves as a source of carbon: Preliminary investigation as catalyst support for electrolytic hydrogen evolution in acidic medium

Our work tends to establish Green Energy from Waste concept. Refuses/wastes can be a secondary resource for variety of materials which may find applications in domestic, industrial, medical, electronic and energy devices. We have attempted to produce activated carbon powders from a cheap waste namely biomass of areca leaves. The material has been exploited as catalyst support materials in H₂ production through water electrolysis. Catalyst powders of 10% Ni and 1% Pt by weight were supported on the carbon produced from the leaves using NaBH₄ reduction of the respective salts. Physical features of the catalyst powders were evaluated through PXRD, FTIR, density, SEM, surface area. Catalytic activity of the biocarbon supported catalyst powders was assessed by LSV & CV. The carbon produced may attract technological importance because carbon source selected is cheap and green. Further the activated carbon may find applications such as electrode materials, adsorbent for color, odor and hazardous pollutants.     

Facile and rapid synthesis of Pt-NiOx/NiF composites as a highly efficient electrocatalyst for alkaline hydrogen evolution

A highly efficient and stable catalyst is the goal of practical electrolysis of water for hydrogen production. Here, Pt-NiO_x nanocomposites anchoring on Ni foam (Pt-NiO_x/NiF) is synthesized by a flexibility galvanic replacement within 2 h and manifests a considerable application prospect for hydrogen evolution reaction (HER) in alkaline media. Owing to the faster kinetics result from appropriate noncovalent interaction, Pt-NiO_x/NiF achieved respectively a factor of 12 and 1.8 enhancement in HER current density relative to NiO_x/NiF and commercial Pt/C at an overpotential of 200 mV. Moreover, such a heterogeneous electrocatalyst have demonstrated a superior long-term stability of 100 h at a high current density of 50 mA/cm². The low cost, easy scalable synthetic strategy and exceptional HER activity makes the industrial application of Pt-NiO_x/NiF possible.