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.     

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.     

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.     

Cellulose nanocrystals (CNC) derived Mo2C@sulfur-doped carbon aerogels for hydrogen evolution

Hydrogen evolution reaction (HER), is considered as an ideal alternative approachs to settle the energy crisis. Therefore, we need to explore efficient and stable non-Pt-based electrocatalysts for hydrogen production from water electrolysis. In this work, S-doped ultrafine molybdenum carbide anchored on cellulose nanocrystals (CNC) derived carbon composite aerogels (Mo₂C@S-CA) were synthesized for HER by a simple one-step carbonization method, utilizing inorganic-organic hybrid ammonium molybdate/CNC (AMM/CNC) as precursor. The obtained Mo₂C@S-CA aerogels can not only provide plenty of active sites, but also accelerate the hydrogen release from the reaction surface of the electrocatalysts. The as-synthesized catalysts exhibit superior HER activity with a small overpotential value of 176 mV vs. RHE at 10 mA cm^?2 and excellent long-term stability after 10,000 cycles in 0.5 M H₂SO₄. These superb properties make the catalyst be a promising electrocatalyst for the HER. This work highlights the importance of biomass-derived multifunctional value-added composite aerogels in enhancing the electrolysis of water.     

M (Co,Ni), N and S tridoped carbon nanoplates as multifunctional catalysts for rechargeable Zn-air batteries and water electrolyzers

Exploration of multifunctional non-precious metal catalysts towards oxygen reduction reaction (ORR), oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is very important for many clean energy technologies. Here, two trifunctional catalysts based on M (Co, Ni), N and S tridoped carbon nanoplates (Co/N/S-CNPs and Ni/N/S-CNPs) are reported. Due to the relatively higher catalytic site content, graphitization degree and smaller charge-transfer resistance, the Co/N/S-CNPs catalyst shows higher activity and stability for ORR (onset potential of 0.99 V and half-wave potential of 0.87 V vs. RHE (reversible hydrogen electrode)), OER (overpotential at 10 mA cm^?2 of 0.37 V) and HER than the Ni/N/S-CNPs catalyst. Furthermore, when constructed with the Co/N/S-CNPs and commercial 20 wt% Pt/C + Ir/C cathodes, respectively, Zn-air battery (ZnAB) based on the Co/N/S-CNPs cathode displays better performance, including a higher power density of 96.0 mW cm^?2 and cycling stability at 5 mA cm^?2. In addition, an alkaline electrolyzer assembled with the Co/N/S-CNPs catalyst as a bifunctional catalyst can reach 10 mA cm^?2 at 1.65 V for overall water splitting and maintain excellent stability even after cycling for 12 h. The present work proves the potential of the Co/N/S-CNPs catalyst for many clean energy devices.     

Three-dimensional structure of WS2/graphene/Ni as a binder-free electrocatalytic electrode for highly effective and stable hydrogen evolution reaction

Tungsten disulfide (WS₂) has attracted much attention as the promising electrocatalyst for hydrogen evolution reaction (HER). Herein, the three-dimensional (3D) structure electrode composed of WS₂ and graphene/Ni foam has been demonstrated as the binder-free electrode for highly effective and stable HER. The overpotential of 3D WS₂/graphene/Ni is 87 mV at 10 mA cm^?2, and the current density is 119.1 mA cm^?2 at 250 mV overpotential, indicating very high HER activity. Moreover, the current density of 3D WS₂/graphene/Ni at 250 mV only decreases from 119.1 to 110.1 mA cm^?2 even after 3000 cycles, indicating a good stability. The high HER performance of 3D WS₂/graphene/Ni binder-free electrode is superior than mostly previously reported WS₂-based catalysts, which is attributed to the unique graphene-based porous and conductive 3D structure, the high loading of WS₂ catalysts and the robust contact between WS₂ and 3D graphene/Ni backbones. This work is expected to be beneficial to the fundamental understanding of both the electrocatalytic mechanisms and, more significantly, the potential applications in hydrogen economy for WS₂.     

Nanoscale engineering MoP/Fe2P/RGO toward efficient electrocatalyst for hydrogen evolution reaction

The preparation of hydrogen evolution reaction (HER) electrocatalyst with high catalytic performance is a huge challenge. In this work, we develop a MoP/Fe₂P/RGO composite as a electrocatalyst for HER. The MoP/Fe₂P/RGO exhibits excellent electrocatalytic performance with a Tafel slope and an onset overpotential of 51 mV/dec and 105 mV, respectively. To drive 10 mA/cm², it only requires a small over-potential of 156 mV. The high electrocatalytic HER activity is mainly due to the synergistic effect of MoP and Fe₂P. In addition, the introduction of RGO not only prevents particle aggregation and coalescence during high temperature phosphating, but also improves the conductivity of the catalyst.     

Porous CoS2 nanostructures based on ZIF-9 supported on reduced graphene oxide: Favourable electrocatalysis for hydrogen evolution reaction

The research and developments of porous, highly active non-noble metal cathode materials are the current hot spots. In our work, ZIF-9 (Zeolitic imidazolate framework-9) as a cobalt source provide porous structure, we have sulfurized the ZIF-9 into CoS₂ by a simple hydrothermal method. Ultimately, the porous CoS₂/RGO cathode material was obtained. Through a series of characterization analyses (powder X-ray diffraction, X-ray photoelectron spectroscopy), it is confirmed that the CoS₂/RGO composite was successfully formed. Furthermore, electrochemical tests demonstrated that the pursued catalyst exhibited remarkable hydrogen evolution reaction (HER) activities with a favorable overpotential (only 180 mV for 10 mA cm^?2 vs reversible hydrogen electrode), a low Tafel slopes (75 mV decade^?1) and high stability in acidic condition (more than 18 h).     

Electrocatalytic hydrogen production on GCE/RGO/Au hybrid electrode

We have prepared a nanocomposite hybrid film to produce a collaborative network of gold (Au) nanoparticles that are highly dispersed on reduced graphene oxide (RGO) sheets, and tested it for electrocatalytic hydrogen production. The RGO/Au nanocomposite film synthesized on glassy carbon electrode (GCE) allows significant improvements to the electron-transfer process. The Au nanoparticles decorated on the surface of graphene increases the electron density, which synergistically promote the adsorption of hydrogen atoms on the graphene sheets and consequently enhance the hydrogen evolution reaction (HER) activity. The surface properties of the composite was characterized by field-emission scanning electron microscopy (FE-SEM) and the electrocatalytical performances evaluated as-prepared electrocatalyst toward (HER) by linear sweep voltammetry (LSV), Tafel polarization curves and electrochemical impedance spectroscopy (EIS) analyses. The GCE/RGO/Au nanohybrid electrode exhibited good catalytic activity for HER with an onset potential of ?0.3 V and a Tafel slope of 136 mV dec^?1, achieving a current density of 10 mA cm^?2 at an overpotential of ?0.43 V.     

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.     

P doped CoMoO4/RGO as an efficient hybrid catalyst for hydrogen evolution

Transition metal oxides, as newly earth-abundant and low-cost catalysts, have been regarded as promising materials for electrocatalytic oxygen evolution. However, they are rarely used as an electrocatalyst in hydrogen evolution reaction (HER) due to the poor HER activity. Herein, we present a facile two-step method to synthesize P doped CoMoO₄/RGO (P-CoMoO₄/RGO) with different atomic ratios of Co²⁺/Co³⁺ through a simple phosphorization strategy by changing the mass of NaH₂PO₂. The effective P-doping into CoMoO₄/RGO can modify the electronic properties and modulate the atomic ratio of Co²⁺/Co³⁺, which promotes the electron transfer and creates more activity sites. Therefore, the optimized P-CoMoO₄/RGO with a relatively larger atomic ratio of Co²⁺/Co³⁺ shows superior HER performances in alkaline media, which affords a current density of 10 mA cm⁻² at a small overpotential of 90 mV and a low Tafel slope of 62 mV dec⁻¹ along with having satisfactory long-term stability. This work provides a valuable route to enhance the HER activity of transition metal oxides.     

Cobalt-molybdenum carbide@graphitic carbon nanocomposites: Metallic cobalt promotes the electrochemical hydrogen evolution reaction

In this work, a series of metallic cobalt-molybdenum carbide@graphitic carbon (CoMo(x:y)-T@GC) nanocomposites for the electrochemical hydrogen evolution reaction (HER) were synthesized by a sol-gel method. In the as-prepared nanocomposites, β-Mo₂C and metallic Co coexisted and were encapsulated by graphitic carbon. The presence of metallic Co effectively enhanced the crystallinity of β-Mo₂C, charge transfer efficiency and electrochemical active surface area (ECSA), thus resulting in the improved HER catalytic activities of the CoMo(x:y)-T@GC nanocomposites. The optimized electrocatalyst CoMo(0.5:0.5)-800@GC required the lowest overpotential of ～165 mV to deliver a current density of 10 mA cm^?2 in 0.1 M KOH, which was at the forefront compared with recently reported Mo₂C-based electrocatalysts.     

Preparation of mesoporous Ni2P nanobelts with high performance for electrocatalytic hydrogen evolution and supercapacitor

The development of bifunctional electrochemically-active materials for both hydrogen evolution reaction (HER) and supercapacitors enables the possibility to integrate energy storage and production into one single system. Here, we report a novel bifunctional mesoporous Ni₂P nanobelt-like architecture prepared via the hydrothermal synthesis of Ni(SO₄)_0.3(OH)_1.4 nanobelt precursor and subsequent low temperature phosphorization process under Ar atmosphere. Composed of numerous cross-linked Ni₂P nanoparticles, the as-obtained Ni₂P nanobelts exhibit a two dimensional leaf-like morphology, allowing remarkable enhancement of mesoporosity as well as active surface area. The HER electrocatalytic test in acid medium show a current density of 16 mA cm^?2 at an overpotential of 187 mV, Tafel slope of 62 mV dec^?1 and long-term durability. Investigation of this Ni₂P nanobelts as supercapacitor materials in 2M KOH electrolyte display a high specific capacity ranging from 1074 F g^?1 at 0.625 A g^?1 to 554 F g^?1 at 25 A g^?1, and notable cycling life with 86.7% retention after 3000 cycles at 10 A g^?1. With the simplicity of the synthetic routine and the outstanding performance as both HER catalysts and supercapacitors, the Ni₂P nanobelts provide promising potential for energy devices.     

Phosphorus-doped nickel sulfides/nickel foam as electrode materials for electrocatalytic water splitting

Hydrogen production from electrocatalytic water splitting is viewed as one of the most promising methods to generate the clean energy. In this work, we successfully prepared an electrode material by growing phosphorus-doped Ni₃S₂ (PNi₃S₂) on nickel foam substrate (NF) under hydrothermal conditions. The phosphorus-doping has an obvious effect on the morphology of Ni₃S₂ on the surface of the nickel foam, which probably results in more active sites, higher electrical conductivity and faster mass transfer. The resulting electrode material displays excellent electrocatalytic activities and stability towards both OER (oxygen evolution reaction) and HER (hydrogen evolution reaction). A relatively low overpotential of 306 mV is required to reach the current density of 100 mA cm^?2 for OER and 137 mV at 10 mA cm^?2 for HER in 1 M KOH solution. When PNi₃S₂/NF was used in an electrolyzer for full water splitting, it can generate a current density of 10 mA cm^?2 at 1.47 V with excellent stability for more than 20 h.     

Highly efficient and stable bifunctional electrocatalyst for water splitting on Fe–Co3O4/carbon nanotubes

Replacement of precious platinum (Pt) or ruthenium oxide (RuO₂) catalysts with efficient, cheap and durable electrocatalysts from earth-abundant elements bifunctional alternatives would be significantly beneficial for key renewable energy technologies including overall water splitting and hydrogen fuel cells. Despite tremendous efforts, developing bifunctional catalysts with high activity at low cost still remain a great challenge. Here, we report a nanomaterial consisting of core-shell-shaped Fe–Co₃O₄ grown on carbon nanotubes (Fe–Co₃O₄/CNTs) and employed as a bifunctional catalyst for the simultaneous electrocatalysts on oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). The Fe–Co₃O₄/CNTs electrocatalyst outperforms the commercial RuO₂ catalyst in activity and stability for OER and approaches the performance of Pt/C for HER. Particularly, it shows superior electrocatalytic activity with lowering overpotentials of 120 mV at 10 mA cm^?2 for HER and of 300 mV at 10 mA cm^?2 for OER in 1 M KOH solution. The superior catalytic activity arises from unique core-shell structure of Fe–Co₃O₄ and the synergetic chemical coupling effects between Fe–Co₃O₄ and CNTs.     

Facile and large-scale preparation of Co/Ni-MoO2 composite as high-performance electrocatalyst for hydrogen evolution reaction

Facile fabrication of high-performance catalyst based on low-cost metals for sustainable hydrogen evolution is still a matter of cardinal significance. However, synthetic approaches for electrocatalyst are usually complicated and the yields are often low. Herein, we report a one-step simple method for the large-scale synthesis of Co/Ni-MoO₂ composite as efficient and stable hydrogen evolution reaction (HER) electrocatalyst to drive 10 mA cm^?2 current density with a low overpotential of 103 mV in basic media. Co-MoO₂ and Ni-MoO₂ were also prepared using this method with overpotential of 137 and 130 mV, respectively, to gain the same current density. These results indicate that this facile synthesis approach is of great practical importance as it can be easily used for large-scale preparation of electrocatalysts in industry.     

Co3Mo3N nanosheets arrays on nickel foam as highly efficient bifunctional electrocatalysts for overall urea electrolysis

Replacing dynamics-restricted oxygen evolution reaction (OER) with smart urea oxidation reaction (UOR) is very important for reducing the power consumption for hydrogen production. Here, the Co₃Mo₃N-400/NF is prepared using a facial way, which exhibits remarkable catalytic performances for UOR, hydrogen evolution reaction (HER) and overall urea electrolysis (OUE) because of the more exposed active sites and high electrical conductivity. At 100 mA/cm², the Co₃Mo₃N-400/NF shows a small potential of 1.356 V vs. RHE (reversible hydrogen electrode) for UOR, which is much lower than that for OER. Furthermore, for HER, to reach to 100 mA/cm², a low overpotential of 299 mV is required, and the urea has negligible influence on the HER process. For OUE, the Co₃Mo₃N-400/NF||Co₃Mo₃N-400/NF shows a small cell potential of 1.481 V at 100 mA/cm² along with a good durability. Our work provides more choice for future OUE to generate hydrogen.     

Electrochemically active and robust cobalt doped copper phosphosulfide electro-catalysts for hydrogen evolution reaction in electrolytic and photoelectrochemical water splitting

The area of non-noble metals based electro-catalysts with electrochemical activity and stability similar or superior to that of noble metal electro-catalyst for efficient hydrogen production from electrolytic and photoelectrochemical (PEC) water splitting is a subject of intense research. In the current study, exploiting theoretical first principles study involving determination of hydrogen binding energy to the surface of the electro-catalyst, we have identified the (Cu_0.83Co_0.17)₃P: x at. % S system displaying excellent electrochemical activity for hydrogen evolution reaction (HER). Accordingly, we have experimentally synthesized (Cu_0.83Co_0.17)₃P: x at. % S (x = 10, 20, 30) demonstrating excellent electrochemical activity with an onset overpotential for HER similar to Pt/C in acidic, neutral as well as basic media. The highest electrochemical activity is exhibited by (Cu_0.83Co_0.17)₃P:30 at. % S nanoparticles (NPs) displaying overpotential to reach 100 mA cm^?2 in acidic, neutral and basic media similar to Pt/C. The (Cu_0.83Co_0.17)₃P:30 at. % S NPs also display excellent electrochemical stability in acidic media for long term electrolytic and PEC water splitting process [using our previously reported (Sn_0.95Nb_0.05) O₂: N-600 nanotubes (NTs) as the photoanode]. The applied bias photon-to-current efficiency obtained using (Cu_0.83Co_0.17)₃P:30 at. % S NPs as the cathode electro-catalyst for HER in an H-type PEC water splitting cell (～4%) is similar to that obtained using Pt/C (～4.1%) attesting to the promise of this exciting non-noble metal containing system.     

Construction of unique NiCo2S4@Ni3V2O8 hierarchical heterostructures arrays on Ni foam as an efficient electrocatalyst with high stability for water oxidation

The development of high efficiency and stable electrocatalysts for the electrochemical water oxidation reaction (WOR) is a grand bottleneck in chemical energy storage and conversion. This article describes a simple co-precipitation route to deposit hierarchical NiCo₂S₄@Ni₃V₂O₈ core/shell hybrid on conductive nickel foam electrode by a simple two-step process. When it is firstly used as the 3D substrates electrode, the NiCo₂S₄@Ni₃V₂O₈ material makes use of both components and provides excellent water oxidation activity, 35 mA cm^?2 was achieved at a overpotential of 290 mV, which is better than the benchmark of IrO₂ electrodes (320 mV of overpotential at 35 mA cm^?2) and 13 mA cm^?2 at 1.47 V with excellent durability. The enhanced water oxidation performance of the NiCo₂S₄@Ni₃V₂O₈ materials is mainly benefiting from its particular core/shell structure, which exhibits big surface areas, and fast electron and ion transfer. Ni₃V₂O₈ shell protects NiCo₂S₄ core from oxidation in the in alkaline electrolytes and improves stability of NiCo₂S₄@Ni₃V₂O₈.This indicates that most metal vanadates oxides-based electrodes are promising as an efficient electrocatalyst and shows the advantages of the interfacial effect, which provide a new idea toward high-performance flexible water oxidation fabrication of robust and cheap catalyst sample.     

Co3O4 nanosheet arrays treated by defect engineering for enhanced electrocatalytic water oxidation

Due to its poor electrical conductivity and finite exposed active sites, the development of high activity Co₃O₄ oxygen evolution reaction (OER) electrocatalysts remains a major challenge. Oxygen vacancies can enhance the electrical conductivity of electrocatalysts and reduce the adsorption energy of H₂O molecules on surfaces, thereby significantly enhancing their electrocatalytic activity. Taking inspiration from this, we demonstrate a green and facile reduction strategy to prepare reduced Co₃O₄ nanosheet arrays (R-Co₃O₄ NSA) with large electrochemical surface area and rich in surface oxygen vacancies. Compared to pristine Co₃O₄ nanosheet arrays (P-Co₃O₄ NSA), R-Co₃O₄ NSA exhibits better OER performance, with a lower overpotential of 330 mV at a current density of 20 mA cm^?2 and a smaller Tafel slope of 72 mV dec^?1. Impressively, the excellent properties of R-Co₃O₄ NSA can rival to the state-of-the-art noble metal oxide electrocatalyst (IrO₂). This strategy of defect-engineering offers a briefness and cost-effective means for the development of highly efficient OER systems.