NiFe layered double hydroxide as an efficient bifunctional catalyst for electrosynthesis of hydrogen peroxide and oxygen

Two electron oxygen reduction reaction to produce hydrogen peroxide (H₂O₂) is a promising alternative technique to the multistep and high energy consumption anthraquinone process. Herein, Ni–Fe layered double hydroxide (NiFe-LDH) has been firstly demonstrated as an efficient bifunctional catalyst to prepare H₂O₂ by electrochemical oxygen reduction (2e^? ORR) and oxygen evolution reaction (OER). Significantly, the NiFe-LDH catalyst possesses a high faraday efficiency of 88.75% for H₂O₂ preparation in alkaline media. Moreover, the NiFe-LDH catalyst exhibits excellent OER electrocatalytic property with small overpotential of 210 mV at 10 mA cm^?2 and high stability in 1 M KOH solution. On this basis, a new reactor has been designed to electrolyze oxygen and generate hydrogen peroxide. Under the ultra-low cell voltage of 1 V, the H₂O₂ yield reaches to 47.62 mmol g_cat^?1 h^?1. In order to evaluate the application potential of the bifunctional NiFe-LDH catalyst for H₂O₂ preparation, a 1.5 V dry battery has been used as the power supply, and the output of H₂O₂ reaches to 83.90 mmol g_cat^?1 h^?1. The excellent electrocatalytic properties of 2e^? ORR and OER make NiFe-LDH a promising bifunctional electrocatalyst for future commercialization. Moreover, the well-designed 2e^? ORR-OER reactor provides a new strategy for portable production of H₂O₂.     

MoS2||CoP heterostructure loaded on N,P-doped carbon as an efficient trifunctional catalyst for oxygen reduction,oxygen evolution,and hydrogen evolution reaction

Exploring multifunctional electrocatalysts is crucial for the development of energy conversion and storage equipments, such as fuel cells, water splitting devices and zinc-air batteries. Herein, we provide a rational design whereby the cobalt phosphide particles are introduced into molybdenum sulfide nanosheets to form a heterostructure (MoS₂||CoP) through the ultrasonic method and calcination. Subsequently, N, P-doped carbon (NPC) is obtained synchronously. The as-prepared MoS₂||CoP/NPC demonstrates highly effective multifunctional catalytic performance for oxygen evolution and hydrogen evolution reaction at lower overpotential, as well as oxygen reduction reaction at high half-wave potential. What this reveals is higher power density and superior stability in zinc-air battery. The excellent electrocatalytic activity of MoS₂||CoP/NPC may be attributed to the presence of the MoS₂||CoP heterostructure, as well as N, P-doped carbon coupled with a high percentage of pyridinic-N. This work proposes a novel and facile strategy to prepare the heterostructure compound and serves as a good reference for constructing efficient and low-cost electrocatalysts.     

Co/Mo2C composites for efficient hydrogen and oxygen evolution reaction

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

Trimetallic PdCuIr nanocages as efficient bifunctional electrocatalysts for polyalcohol oxidation and hydrogen evolution reaction

Despite amounts of researches in recent years, it is still desirable but challenging to fabricate well-defined bifunctional catalysts with high performance towards alcohol oxidation and hydrogen evolution reaction (HER). Herein, a unique trimetallic PdCuIr catalyst with a nanocage (NC) structure is synthesized to be an excellent bifunctional catalyst by a seed-mediated growth strategy. The as-prepared PdCuIr NC catalyst exhibits remarkably enhanced mass activity and durability towards glycerol oxidation reaction (GOR) and ethylene glycol oxidation reaction (EGOR) as compared with commercial Pd/C catalyst. The optimal Pd₅₈Cu₃₂Ir₁₀ NCs show electrocatalytic activities of 2565.79 mA mg_Pd⁻¹ and 4498.30 mA mg_Pd⁻¹ for GOR and EGOR, respectively. Meanwhile, the well-defined PdCuIr NC catalyst also displays outstanding electrocatalytic performance for HER, and the overpotential of Pd₅₈Cu₃₂Ir₁₀ NCs only requires 54 mV to arrive at a current density of 10 mA cm⁻², along with excellent electrochemical durability. The enhancement of electrocatalytic properties is attributed to the introduction of Cu and Ir atoms, which could modify the electronic structure of Pd to optimize the adsorption of reactants and intermediates. Moreover, the unique NC structure also significantly increases the number of reaction active sites as well as accelerates mass transport. Following this method, the trimetallic PdCuRu NCs and PdCuRh NCs are also synthesized. This work not only offers a general strategy for the fabrication of well-defined ternary alloy nanocatalysts, but also presents an advanced class of bifunctional catalysts for polyalcohol electrooxidation and HER.     

Preparation of ultrathin molybdenum disulfide dispersed on graphene via cobalt doping: A bifunctional catalyst for hydrogen and oxygen evolution reaction

The development of highly active and low-cost catalysts for hydrogen evolution reaction (HER) is significant for the development of clean and renewable energy research. Owing to the low H adsorption free energy, molybdenum disulfide (MoS₂) is regarded as a promising candidate for HER, but it shows low activity for oxygen evolution reaction (OER). Herein, graphene-supported cobalt-doped ultrathin molybdenum disulfide (Co–MoS₂/rGO) was synthesized via a one-pot hydrothermal method. The obtained hybrids modified electrode exhibits a high HER catalytic activity with a low overpotential of 147 mV at the current density of 10 mA cm⁻², a small Tafel slope of 49.5 mV dec⁻¹, as well as good electrochemical stability in acidic electrolyte. Meanwhile, the catalyst shows remarkable OER activity with a low overpotential of 347 mV at 10 mA cm⁻². The superior activity is ascribed not only to the high conductivity originated from the reduced graphene, but also to the synergistic effect between MoS₂ and cobalt.     

Cobalt phosphide nanoparticles embedded in 3D N-doped porous carbon for efficient hydrogen and oxygen evolution reactions

An electrocatalyst based on a unique three-dimensional (3D) N-doped porous carbon sheet networks embedded with CoP₂ nanoparticles (CoP₂@3D-NPC) was synthesized by a facile pyrolysis process as well as an in-situ phosphatization method. The improved CoP₂@3D-NPC hybrid materials show excellent electrocatalytic activity toward HER and OER. This material provides a low overpotential of 126 mV at 10 mA cm⁻² in 0.5 M H₂SO₄ and 167 mV at 20 mA cm⁻² in 1.0 M KOH for HER with a small Tafel slope value of 59 mV dec⁻¹, respectively. Besides, it is also active for the OER under alkaline conditions. Such a prominent property of the CoP₂@3D-NPC electrocatalyst could be attributed to its excellent electrical conductivity of 3D carbon substrate, strong synergistic effect between CoP₂ nanoparticles and carbon nanosheet as well as extra active sites created by the N-doped structure.     

Ni3Mo3N coupled with nitrogen-rich carbon microspheres as an efficient hydrogen evolution reaction catalyst and electrochemical sensor for H2O2 detection

Hydrogen evolution reaction (HER) and electrochemical analysis are two important fields of electrochemical research at present. We found that both HER and some electrochemical analytical reactions relied on the concentration of hydrogen ions (H⁺) in solution, so we intended to develop an electrode material that is sensitive to H⁺ and can be used for both HER and some electrochemical analyses. In this work, we synthesized Ni₃Mo₃N coupled with nitrogen-rich carbon microspheres (Ni₃Mo₃N@NC MSs) as highly efficient electrode material for HER and detection of Hydrogen peroxide (H₂O₂), which plays an important role in physiological processes. Here the aniline was used as the nitrogen and carbon sources to synthesize Ni₃Mo₃N@NC. The Ni₃Mo₃N@NC MSs showed high performance for HER in 1 M KOH solution with a small overpotential of 51 mV at 10 mA cm^?2 and superior stability. For H₂O₂ detection, a detection limit of 1 μM (S/N = 3), sensitivity of 120.3 μA·mM^?1 cm^?2 and linear range of 5 μM–40 mM can be achieved, respectively. This work will open up a low-cost and easy avenue to synthesize transition metal nitrides coupled with N-doped carbon as bifunctional electrode material for HER and electrochemical detection.     

CeO2 nanoparticle-decorated reduced graphene oxide as an efficient bifunctional electrocatalyst for oxygen reduction and evolution reactions

Highly efficient bifunctional electrocatalysts for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are essential for the development of renewable energy technologies such as fuel cells and metal-air batteries. Herein, a ceria (CeO₂) – modified reduced graphene oxide (CeO₂/rGO) nanocomposite was fabricated via a facile yet cost-effective method under a mild condition. The prepared CeO₂/rGO nanocomposite showed remarkable catalytic activity, high tolerance to methanol and durability toward ORR in alkaline media. Meanwhile, the catalyst also displayed remarkable activity for the OER with more negative onset potential and higher current compared with commercial Pt/C catalyst. The high oxygen reaction activity of the catalyst could contribute to synergistic effect of the combination of the oxygen vacancies of CeO₂ and excellent electronic conductivity of rGO. The results suggested that the CeO₂/rGO nanocomposite has potential advantages as a bifunctional electrocatalyst in the practical applications.     

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.     

N-enriched porous carbon doped with co,ni, and Mo as efficient electrocatalyst for hydrogen evolution reaction

Splitting water for hydrogen production is still a promising technique to meet the energy requirements of society and overcome many environmental problems. However, the development of carbon-based transition electrocatalysts with superior activity for hydrogen evolution reaction (HER) is still challenging. In this study, a CoNiMo/NPC electrocatalyst was successfully fabricated using ZIF-67 as a precursor via facile absorption, pyrolysis and annealing processes. The fabricated CoNiMo/NPC was used as an electrocatalyst for hydrogen production. The results revealed that the doping of Ni and Mo increase the number of active sites and enhance the conductivity of electrocatalysts. CoNiMo/NPC exhibits excellent HER activity in alkaline solutions and only requires an overpotential of 182 mV to reach a current density of 10 mA/cm². Furthermore, long-term measurements demonstrated that CoNiMo/NPC has superior durability in alkaline solutions. The excellent HER performance of CoNiMo/NPC can be attributed to the doping of Co, Ni, and Mo on porous carbon. In addition, the high specific surface area and high graphitisation degree of the electrocatalyst are beneficial for rapid charge transport and collection.     

Three-dimensional flower-like Co-based metal organic frameworks as efficient multifunctional catalysts towards oxygen reduction,oxygen evolution and hydrogen evolution reactions

Design and development of cost-efficient multifunctional three-dimensional (3D) metal organic frameworks (MOFs) towards oxygen reduction reaction (ORR), oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) are very significant for green energy devices. Herein, a scalable one-pot solvothermal method is developed to obtain a series of multifunctional 3D flower-like MOFs. In addition, systematic studies are also conducted on the effects of various metal cations and N-containing ligands on the structures, compositions, and multifunctional performance of the obtained MOFs. As a result, 3D flower-like Co-MOFs using Co²⁺ as a metal cation and 2,2’:6′,2″-terpyridine as a N-containing ligand exhibit the highest multifunctional performance towards ORR, OER and HER. The scalable method provides a new prospect to design and develop other MOFs-based multifunctional catalysts.     

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.     

Hollow ZnxCo1-xSe2 microcubes derived from Metal–Organic framework as efficient bifunctional electrocatalysts for hydrogen evolution and oxygen evolution reactions

Herein, we designed a simple and universal method to prepare cobalt-based bimetallic Zn_xCo_1-x-MOFs precursors, which were used as templates to synthesize effective bifunctional electrocatalyst hollow porous Zn_xCo_1-xSe₂ microcubes by one-step hydrothermal method. The cubic morphology of the Zn_xCo_1-x-MOFs precursors was well inherited. Particularly, the Zn_0.1Co_0.9Se₂ exhibited superior HER and OER performance in acidic solution and alkaline solution, respectively. Benefiting from the hollow porous structure, the synergistic effect of Zn–Co–Se and the incorporation of a small number of zinc atoms.

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Platinum nanoparticles decorated Nb2CTx MXene as an efficient dual functional catalyst for hydrogen evolution and oxygen reduction reaction

Here, a dual functional Nb₂CT_x@Pt nanocomposite has been synthesized by in situ reduction method. The Pt loading in the composite has been optimized to get minimum overpotential (141 mV at 10 mA/cm²) for hydrogen evolution reaction (HER) along with a promising Tafel slope of 46.3 mV/dec, while Pt/C shows an overpotential and Tafel slope of 104 mV and 32.4 mV/dec, respectively. The Pt mass activity for Nb₂CT_x@Pt3.8 composite at 100 mV overpotential was 3.44 A g^?1 while the Pt mass activity for conventional Pt/C was 0.7 A g^?1, which shows that the activity of Nb₂CT_x@Pt3.8 composite is approximately 5 times higher than Pt/C. In addition, the catalyst was found to be stable for continuous 500 cycles without any binder molecules. The oxygen reduction reaction (ORR) capability of the material was also evaluated and found that the catalyst exhibited a current density of ?4.28 mA/cm² in the diffusion limiting region in comparison with the current density of ?5.82 mA/cm² for Pt/C at 2600 revolutions per minute (RPM). The Pt mass activity of Nb₂CT_x@Pt3.8 composite for ORR is approximately 10 times higher than Pt/C. The Nb₂CT_x@Pt3.8 composite was able to reduce O₂ completely using the 4-electron pathway with very little peroxide production. From these results, the dual functionality of the Nb₂CT_x@Pt3.8 composite for both HER and ORR has been established.     

Fabrication of nanoporous gold-islands via hydrogen bubble template: An efficient electrocatalyst for oxygen reduction and hydrogen evolution reactions

In this report, the fabrication of a high surface area nanoporous gold-island (NPG-islands) onto a glassy carbon (GC) surface by a simple one-step electrodeposition procedure based on a dynamic hydrogen bubble template method is described. The surface morphology, purity and crystalline structure of the porous NPG-islands were analyzed by field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray analysis (EDX), and X-ray diffraction (XRD) techniques. Cyclic voltammetry and linear sweep voltammetry methods were used for electrochemical studies and the electrocatalytic activity of the NPG-islands surface was investigated towards the oxygen reduction reaction (ORR) and hydrogen evolution reaction (HER). Electrochemical results revealed exceptional ORR activity of the NPG-islands evaluated by the shift of the onset potential towards less negative values compared to bare GC (0.55 V) and Au (0.25 V) electrodes, respectively, with a 3-fold increased current density in neutral PBS solution (pH 7). Rotating-disk measurements indicate a direct conversion of oxygen to water via a four-electron reduction pathway. The electrocatalytic activity was also evaluated for HER in 0.5 mol L⁻¹ H₂SO₄ solution and a benchmark current density of 10 mA cm⁻² at a very low overpotential of −0.075 V was obtained, which is similar to bulk Pt performance. The plausible mechanism of the HER was realized from the Tafel plot and the obtained slope of 46 mV dec⁻¹ suggests the Volmer-Heyrovsky mechanism takes place in such electrochemical process. Furthermore, the durability of the catalyst was also studied and exceptional stability was observed in cyclic voltammetry (up to 2000 cycles) and chronopotentiometry (at 10 mA cm⁻² for 19 h).     

3D hierarchical network NiCo2S4 nanoflakes grown on Ni foam as efficient bifunctional electrocatalysts for both hydrogen and oxygen evolution reaction in alkaline solution

The development of cost-effective and high-efficiency electrocatalysts for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) still remains highly challenging. Exposing as many active sites as possible is the key method to improve activity of HER and OER performance. In this communication, we demonstrate a novel 3D hierarchical network NiCo₂S₄ nanoflake grown on Ni foam (NiCo₂S₄-NF) as a highly efficient and stable electrochemical catalyst. The NiCo₂S₄-NF exhibits overpotentials as low as 289 and 409 mV at 100 mA cm^?2, superior long-term durability during a 20 h measurement, and a low Tafel slope of 89 and 91 mV dec^?1 for HER and OER in 1.0 M NaOH solution. The outstanding performance is owe to the inherent activity of ultrathin NiCo₂S₄ nanoflakes and the special structure of NiCo₂S₄-NF that can provide a huge number of exposed active sites, accelerate the transfer of electrons, and facilitate the diffusion of electrolyte simultaneously.     

ZIF-67-derived Mn doped Co9S8 supported on N-Enriched porous carbon polyhedron as an efficient electrocatalyst for oxygen evolution reaction

Rational design of efficient oxygen evolution reaction (OER) electrocatalysts plays a significant role in various applications like water splitting and metal-air batteries. Simultaneous modulation of geometric and electronic structure is a promising strategy for boosting the electrocatalytic active of OER catalysts. Herein, a novel type of Mn doped Co₉S₈ supported on N-enriched porous carbon polyhedron composite material (Mn–Co₉S₈/NC) is constructed via absorption-pyrolysis-sulfurization treatment of Zeolitic-imidazolate frameworks (ZIF-67). ZIF-67 derived N-enriched porous carbon polyhedron serves as the porous skeleton for anchoring numerous Co₉S₈ nanoparticles. The results confirm that the incorporation of Mn in Co₉S₈/NC can improve the degree of graphitization compared with Co₉S₈/NC, implying the enhancement of the conductivity. Meanwhile, the incorporation of Mn can lead to electronic modulation of Co species to bump up the intrinsic activity of active site in Mn–Co₉S₈/NC. Due to the synergistic effect of Mn, Co₉S₈ and porous carbon structure, the specific surface area and electronic structure are optimized, endowing the maximum utilization of active sites. The Mn–Co₉S₈/NC electrocatalyst exhibits superior OER activity with the overpotential of 286 mV at current density of 10 mA cm⁻² in 1.0 M KOH electrolyte. This work provides prospective insights into the synergistic coupling of geometric and electronic structure of Metal-Organic Frameworks (MOFs) material for efficient electrocatalysts.     

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

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

WSe2/rGO hybrid structure: A stable and efficient catalyst for hydrogen evolution reaction

The number of exposed active sites in a catalyst plays a key role in determining its catalytic performance. However, the aggregation effect in nanostructured catalysts causes much less reactive sites exposed. In this paper, we report a novel structure of WSe₂/rGO with highly exposed WSe₂ active edge sites by uniformly imbedding the rGO between each WSe₂ nanosheets. With the introduction of rGO, the electron transport property of the WSe₂/rGO hybrid structure has also been enhanced. The structure and composition of the samples were investigated by the X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and transmission electron microscopy. Our electrochemical characterizations confirm that the WSe₂/rGO hybrid structure exhibits enhanced electrochemical catalytic performance with a Tafel slop of 85 mV/dec for HER, much smaller than that of the pure WSe₂.