In situ synthesis of a novel organic-inorganic composite as a non-noble metal electrocatalyst for the oxygen evolution reaction

Offering new techniques for efficient design and fabrication of inexpensive and earth-abundant catalysts for the development of oxygen evolution electrodes is a fundamental approach to promote sustainable energy processes. Herein, we report the in situ synthesis of a novel organic-inorganic composite directly onto carbon paste electrode (CPE) surface, as a robust substrate to incorporate Nickel-Iron (Ni-Fe) metal ions without using any binders or energy consumer techniques. Polyoxometalate (POM) and o-Anisidine (oA) are composite components that can be easily combined on the electrode surface (oA-POM/CPE). Ascribed to the synergy of context and metal ions, the as-prepared electrode affords a high catalytic activity and stability towards oxygen evolution reaction (OER), and gained a current density of 10 mA cm^?2 at overpotential of 330 mV. Moreover, the distinct electrocatalytic activity is illustrated by varying the amount of Fe in immersion solution, which proves the change made in percentage ratio of Ni-Fe in immersion solution that consequently affects Ni-Fe percentage value on electrode surface. This represents the competition between metal cations in creating complex with composite. Collectively, this simple strategy provides a promising way for the development of effective and non-noble metal-based OER electrocatalysts.     

Defective layered NiFe double hydroxides anchored on self-supported CoNi-nitrogen doped carbon nanotube composite as advanced electrocatalyst for oxygen evolution reaction

Oxygen evolution reaction (OER) is an essential process during electrochemical water-splitting. Due to its sluggish kinetics, low cost and highly efficient catalyst is invariably desired to decrease its overpotential for large-scale application. However, the overpotential of most advanced OER electrocatalysts is still more than 200 mV at the current density of 10 mA cm^?2. In this work, we constructed active layered NiFe double hydroxides with cation defects on self-supported three-dimensional (3D) CoNi nitrogen-doped carbon nanotube composite substrate as integrated OER catalyst. Strikingly, electrochemical measurements showed that the optimized sample exhibited outstanding OER activity with low overpotentials of 178 and 268 mV at the current densities of 10 and 100 mA cm^?2 in alkaline environment, alongside a good durability. The excellent OER performance was ascribed to the strongly synergistic effect of intrinsically active NiFe double hydroxide layers with abundant cation vacancies and 3D carbon nanotube composite substrate with good conductivity and various functional moieties, thus facilitating the electrocatalytic kinetic.     

Ir-doped Co3O4 as efficient electrocatalyst for acidic oxygen evolution reaction

Oxygen evolution reaction (OER) is an important bottleneck for large-scale acidic water splitting applications due to its sluggish reaction kinetics. Therefore, the development of highly active, stable, and inexpensive electrocatalysts for OER remains a challenge. Herein, we develop the iridium doped Co₃O₄ (Ir–Co₃O₄) with low Ir content of 2.88 wt% for efficient acidic OER. Considering systemic characterizations, it is probably concluded that Ir can be uniformly doped into the lattice of Co₃O₄ and induce a certain distortion. The electrochemical results reveal that Ir–Co₃O₄ nanoparticles demonstrate significantly enhanced electrocatalytic OER activity and stability in 0.5 M H₂SO₄ solution compared with pure Co₃O₄, in which the overpotential at the current density of 10 mA cm⁻² decreases from 382 mV to 225 mV and the value of Tafel slope decreases from 101.7 mV dec⁻¹ to 64.1 mV dec⁻¹. Besides, Ir–Co₃O₄ exhibits excellent electrocatalytic durability for continuous 130 h's test without any activity attenuation. Moreover, this work provides a kind of high-performance acidic OER electrocatalyst for the development of hydrogen energy.     

NiCoFe oxide amorphous nanohetrostructres for oxygen evolution reaction

Two dimensional (2D) nanohetrostructures (NHS) composed of multimetal oxide nanoparticles (NPs) with site selective growth on either basal or lateral of the 2D multimetal oxide nanosheets (NSs) substrate are highly desirable due to their unique chemical and physical properties but extremely challenging in preparation. Herein, for the first time, we demonstrate the rational control growth of amorphous NiCoFeOx NPs on either lateral or basal of amorphous NiCoFeOx NSs by hydrothermal method. Owing to the lateral growth of amorphous NiCoFeOx NPs on the amorphous NiCoFeOx NSs, this unique architecture exhibits more electrocatalytic active sites and better stability due to higher In-plane conductivity than interlayer conductivity. Furthermore, density functional theory (DFT) calculation shows that due to the presence of low coordinated oxygen, it decreased the energy barrier of intermediates and enhanced the oxygen evolution reaction (OER) performance. While, NiCoFe oxide NHS with lateral growth of NiCoFeOx NPs lead to superior electrocatalytic activity toward oxygen evolution reaction (OER) with a low overpotential of 232 mV to reach a current density of 10 mAcm⁻², due to the amorphous nature of NHS, synergistic effect, conductive support (like Nickel Foam) with metal oxide substrate. Furthermore, employing Lateral growth NHS as an anode and cathode for water splitting electrolyzer able to reach 10 mAcm⁻² at a cell voltage of 1.49 V with robust durability. This work will provide a new dimension for the construction of other site selective 2D NHS with unique properties especially for OER.     

Se-doped cobalt oxide nanoparticle as highly-efficient electrocatalyst for oxygen evolution reaction

Electrolysis of water has been one of the most promising approaches for renewable energy resources while the efficient oxygen evolution reaction (OER) remains challenging. Herein, a series of different ratio of Se doped Co₃O₄ nanoparticles XSe-Co₃O₄ are prepared by hydrothermal method and applied as OER electrocatalysts. Se^2? is doped into the Co₃O₄ crystal lattice by substituting of O^2? and a large number of oxygen vacancies are generated, which provides more available activity sites for OER. Se doping increases the surface ratio of Co²⁺/Co³⁺ and accelerates the electron transport that favors OER activity promotion. The optimized doping ratio of 6%Se–Co₃O₄ presents low overpotential of 281 mV at 10 mA cm^?2, as well as a low Tafel slope of 70 mV dec^?1 in 1 M KOH solution, which has great advantages compared to the recently reported Co₃O₄-based OER electrocatalysts. This work provides new ideas for the development of efficient Co₃O₄-based OER electrocatalysts.     

Boron doped cryptomelane as a highly efficient electrocatalyst for the oxygen evolution reaction

In this study, cryptomelane-type (1D) MnO₂ was doped with boron powder by ball-milling in an inert organic solvent under various experimental conditions. The structural, thermal, morphological, and surface features of samples prepared by the ball-milling method were characterized by powder X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, X-ray photoelectron spectroscopy, scanning and transmission electron microscopy, and surface measurements. The electrocatalytic oxygen evolution reaction (OER) performances of the samples were tested and compared with the bare cryptomelane to reveal the effect of boron doping into manganese oxide. It was found that boron particles transformed to trigonal BO₃ units in the cryptomelane structure via mechanical activation, and accordingly, the oxidation state of manganese in this structure relatively changed. The 0.25% B-doped cryptomelane sample prepared at 12 h grinding time exhibited the overpotential of 425 mV at a current density of 1 mAcm⁻² with a Tafel slope of ∼95 mV dec⁻¹. It showed a remarkable catalytic performance among the other electrocatalysts under neutral pH compared to bare cryptomelane. When the elemental boron doping exceeded 1%, the electrochemical performance dramatically decreased depending on the blocking of the Mn³⁺ active sites.     

Facile synthesis of IrO2 nanoparticles decorated @ WO3 as mixed oxide composite for outperformed oxygen evolution reaction

Oxygen evolution reaction (OER) electrocatalysts play the critical role in efficiency and durability for different hydrogen production systems. We have successfully synthesized the earth abundant WO₃ coupled with IrO₂ as mixed oxide composite by a facile two-step chemical method. 50% reduction in noble metal contents (IW-50) followed by two times enhancement in activity, four-folds increase in bulk mass specific activity along with the stability of mixed oxide composite as compared to state –of –the art IrO₂ catalyst are affirmed. Superior performance of mixed oxide composites are perceived due to four times increase in electrochemical surface area, reduction of Tafel slope, four-fold increase of turn over frequency, electronic distortion in Ir-4f spectrum of IW-50 along with the bridging of lattice oxygen atoms between iridium and tungsten metals. We believe that it would open up the new avenues for effective utilization of noble metal with high valence tungsten metal in corrosive environment.     

Reduced CoFe2O4/graphene composite with rich oxygen vacancies as a high efficient electrocatalyst for oxygen evolution reaction

Oxygen evolution reaction (OER) is regarded as a limit-efficiency process in electrochemical water splitting generally, which needs to develop the effective and low-cost non-noble metal electrocatalysts. Oxygen vacancies have been verified to be beneficial to enhance the electrocatalytic performance of catalysts. Herein, we report the facile synthesis of reduced CoFe₂O₄/graphene (r-CFO/rGO) composite with rich oxygen vacancies by a citric acid assisted sol-gel method, heat treatment process and the sodium borohydride (NaBH₄) reduction. The introduction of graphene and freezing dry technique prevents the restacking of GO and the aggregation of CFO nanoparticles (NPs) and increases the electronic conductivity of the catalyst. Fast heating rate and low anneal temperature favors to obtain low crystallinity and lattice defects for CFO. NaBH₄ reduction treatment further creates the rich oxygen vacancies and electrocatalytic active sites. The obtained r-CFO/rGO with high specific surface area (108 m² g⁻¹), low crystallinity and rich oxygen vacancies demonstrates a superior electrocatalytic activity with the smaller Tafel slope (68 mV dec⁻¹), lower overpotential (300 mV) at the current density of 10 mA cm⁻², and higher durability compared with the commercial RuO₂ catalyst. This green, low-cost method can be extended to fabricate similar composites with rich defects for wide applications.     

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.     

Large-area manganese oxide nanorod arrays as efficient electrocatalyst for oxygen evolution reaction

Large-area manganese oxide nanorod arrays (MnO₂ NRAs) have been directly grown vertically on Ti foil with a uniform length and diameter by a simple electrochemical method without any templates. The deposition temperature is one of the most important parameters for formation MnO₂ NRAs and at 25 °C no MnO₂ NRAs can be obtained. The results show that MnO₂ has high activity and good stability for oxygen evolution reaction (OER) and the structure of nanorod arrays pronounced enhances MnO₂ activity. The onset potential of MnO₂ NRAs is lower than that of Pt foil and lower 401 mV than that of MnO₂ film, indicating that the structure of MnO₂ NRAs shows an easy OER for water split. The MnO₂ NRAs may be of great potential in electrochemical water split.     

Nitrogen doped amorphous carbon as metal free electrocatalyst for oxygen reduction reaction

A non metal catalyst for the oxygen reduction reaction is prepared by simply pyrolyzing ion exchange resin D113 in NH₃. The product is nitrogen doped amorphous carbon. The pyrolysis of D113 exchanged with iron ion results in nitrogen doped graphitic carbon. The amorphous carbon is easier to be doped by NH₃ with higher nitrogen content. The nitrogen doped amorphous carbon is more active than graphitized carbon, together with much improved stability. The higher activity is explained by the higher total nitrogen content and higher pyridinic/graphitic nitrogen percentage. The higher stability is because there is no loss or dissolution of the active sites. The results of this work prove metal element and graphitization of carbon are not necessary factors for nitrogen doped carbon as non noble metal catalyst for the oxygen reduction reaction.     

Manganese oxide with different morphology as efficient electrocatalyst for oxygen evolution reaction

Three-dimensional (3D) manganese oxides consisted of tetragonal phase Mn₃O₄ and α-MnO₂ with different morphology have been directly grown vertically on Ti foil by a simple electrochemical method without any template and used as the catalysts for oxygen evolution reaction (OER). The results show that manganese oxides with different morphology show high activity and good stability for OER and the manganese oxide (MnO_x) nanowire arrays obtained at 70 °C show higher activity and better stability than MnO_x with cotton wool structure and MnO_x nanosheet arrays.     

Fe doped metal organic framework (Ni)/carbon black nanosheet as highly active electrocatalyst for oxygen evolution reaction

To alleviate the sluggish oxygen evolution reaction (OER) kinetics, it's urgent to develop electrocatalysts with high activity and low cost. In this work, Fe doped metal organic frameworks (Ni)/carbon black composites were synthesized via a facile hydrothermal method. Benefiting from the direct use of metal organic frameworks (MOFs) for OER, numerous and highly dispersed active sites are exposed to the electrolyte and reactants. By regulating Ni/Fe ratios, a high electrochemical active surface area (ECSA) and high relative surface content of active Ni³⁺ species are obtained, which mainly contribute to the high OER activity. Besides, the introduced carbon black (CB) was found to enhance the charge-transfer efficiency of the electrocatalysts, which is also favorable for OER. The optimal Ni9Fe1-BDC-0.15CB electrocatalyst shows excellent OER activity with the low overpotential of ~290 mV at 10 mA cm⁻² and the Tafel slope of ~76.1 mV dec⁻¹, which is comparable to RuO₂ and other MOFs-based OER electrocatalysts reported in recent years.     

Facile and scalable synthesis of heterostructural NiSe2/FeSe2 nanoparticles as efficient and stable binder-free electrocatalyst for oxygen evolution reaction

Oxygen evolution reaction (OER) is a rate-limiting step in electrocatalytic water splitting due to its sluggish reaction kinetics. Therefore, it is still challengeable to develop an inexpensive and efficient OER catalyst via a facile and scalable synthesis method. To address such issues, herein, we present a facile and scalable approach to prepare ultrathin NiSe₂/FeSe₂ heterostructural nanoparticles in-situ grown on NiFe foam (NFS/NFF), which can be employed as a self-supported non-noble metal-based catalyst for OER. The NFS/NFF catalyst delivers outstanding OER performance with a small Tafel slope of 57.07 mV dec⁻¹ and a low overpotential of 274 mV at 40 mA cm⁻² and displays terrific long-term stability, surpassing the performance of commercial RuO₂ and single component NiSe₂/NF catalyst. The results of XPS manifest that there is a strong heterointerface interaction between NiSe₂ and FeSe₂. In addition, combined with density functional theory (DFT) calculations, we further confirmed that the synergistic interface effect between NiSe₂ and FeSe₂ reduces the value of the Gibbs free energy of oxygen-containing intermediates as determining step (RDS) from 3.15 eV (NiSe₂) to 2.41 eV (NiSe₂/FeSe₂ heterostructures), leading to excellent OER performance. This work provides a novel strategy to rationally design and fabricate selenide-based heterostructural nanoparticles via a facile method, which can extend to prepare other non-precious OER catalysts with high efficiency and long-term stability.     

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.     

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.     

Controlled synthesis of NiCo2O4@Ni-MOF on Ni foam as efficient electrocatalyst for urea oxidation reaction and oxygen evolution reaction

Heterostructured materials with special interfaces and features give a unique character for much electrocatalytic process. In this work, the introduction of exogenous modifier Ni-MOF improved the reaction kinetics and morphology of the NiCo₂O₄@Ni-MOF/NF catalyst. As-obtained NiCo₂O₄@Ni-MOF/NF has excellent oxygen evolution reaction (OER) performance and urea oxidation reaction (UOR) performance. The catalyst need overpotential of 340 mV at a current density of 100 mA cm^?2 for OER and a potential of 1.31 V at the same current density for UOR. The Tafel slopes of NiCo₂O₄@Ni-MOF/NF is 38.34 and 15.33 mV dec^?1 for OER and UOR respectively, which is more superior than 78.58 and 66.73 mV dec^?1 of NiCo₂O₄/NF. The nanosheets microstructure is beneficial to the adsorption and transport of electrolyte and the presence of a large number of mesoporous channels can also accelerate gas release, and then improves activity of the catalyst. Density functional theory calculation demonstrate that NiCo₂O₄ plays a role in absorbing water, while the existence of in situ generated NiOOH can promote the electron transfer efficiency. It is synergies of NiCo₂O₄ and in situ generated NiOOH that enhance the decomposition of water on the surface of the NiCo₂O₄@Ni-MOF/NF. This investigation provides a new strategy for the application of spinel oxide and MOF materials.     

Oxygen vacancy-based ultrathin Co3O4 nanosheets as a high-efficiency electrocatalyst for oxygen evolution reaction

Enhancing the catalytic activity of Co₃O₄ electrocatalysts featuring abundant oxygen vacancies is required to enable their application in oxygen evolution reaction (OER). However, developing a harmless defect engineering strategy based on mild conditions to realize such an enhancement remains a challenge. Here, ultrathin Co₃O₄ nanosheets with abundant oxygen vacancies were prepared through a simple two-step method comprising a hydrothermal process and pre-oxidation to study the catalytic activity of the nanosheets toward OER. The ultrathin sheet structure and the Co₃O₄ nanosheets surface provide abundant active sites. The oxygen vacancy not only improves the catalyst activity, but also improves the electron transfer efficiency. These advantages make ultrathin Co₃O₄ nanosheets with abundant oxygen vacancies an excellent electrocatalyst for oxygen evolution. In an alkaline medium, ultrathin Co₃O₄ nanosheets exhibited excellent OER catalytic activity, with a small overpotential (367 mV for 10 mA/cm²) and faster reaction kinetics (65 mV/dec).Moreover, the electrocatalyst still maintained 68% of its original catalytic activity after 24 h operation. This work provides an extensive and reliable method for the preparation of low-cost and highly efficient OER electrocatalysts.     

Electrosynthesis of Mn-Fe oxide nanopetals on carbon paper as bi-functional electrocatalyst for oxygen reduction and oxygen evolution reaction

A layered binary Mn-Fe oxide as bi-functional electro-catalyst with nanopetals morphology is grown on porous carbon paper for the first time via one-step electrodeposition process. The electrocatalyst is characterized by X-ray diffraction, scanning electron microscopy (SEM) and energy dispersive spectroscopy analysis. SEM analysis demonstrates notable morphology viz. nanopetals of the Mn-Fe oxide grown on carbon paper. The electrocatalytic activity is checked for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline medium. Rotating disk electrode (RDE) voltammetry is carried out to study the ORR kinetics, which proves that ORR process follows four-electron pathway in alkaline medium. Oxygen evolution reaction study reveals that it has higher activity for OER with a lower onset potential of 1.6 V vs RHE and higher current density of 11.5 mA/cm² at 2.0 V vs RHE reference electrode.     

Phase pure synthesis of iron-nickel nitride nanoparticles: A low cost electrocatalyst for oxygen evolution reaction

Synthesis of mixed transition metal nitrides often leads to the formation of more than one phases in the final product. A control over molar ratio of metals (Fe:Ni) along with synthetic strategy is used to form phase pure product (Fe₃Ni₇N@C). The synthesized material is used as an efficient and cost-effective electrocatalyst for oxygen evolution reaction (OER). Fe₃Ni₇N@C requires a low overpotential of 290 mV to achieve a catalytic current density of 10 mA cm⁻² which holds Tafel slope of 40 mV dec⁻¹ superior to the noble metal benchmark catalysts. The physicochemical integrity of Fe₃Ni₇N@C is maintained up to 12 h activity as evident from post catalytic characterization.