Electronic regulation and core-shell hybrids engineering of palm-leaf-like NiFe/Co(PO3)2 bifunctional electrocatalyst for efficient overall water splitting

Constructing efficient and stable bifunctional electrocatalysts for overall water splitting remains a challenge because of the sluggish reaction kinetics. Herein, the core-shell hybrids composed of Co(PO₃)₂ nanorod core and NiFe alloy shell in situ grown on nickel foam (NiFe/Co(PO₃)₂@NF) are synthesized. Owing to the hierarchical palm-leaf-like structures and strong adhesion between NiFe alloys, Co(PO₃)₂ and substrates, the catalyst provides a large surface area and rapid charge transfer, which facilitates active sites exposure and conductivity enhancement. The interfacial effect in the NiFe/Co(PO₃)₂ core-shell structure modulates the electronic structure of the active sites around the boundary, thereby boosting the intrinsic activity. Benefiting from the stable structure, the durability of the catalyst is not impaired by the inevitable surface reconfiguration. The NiFe/Co(PO₃)₂@NF electrode presents a low cell voltage of 1.63 V to achieve 10 mA cm^?2 and manifests durability for up to 36 h at different current densities.     

Structure engineering of amorphous P–CoS hollow electrocatalysts for promoted oxygen evolution reaction

Oxygen evolution reaction (OER) is a key process involved in many energy-related conversion systems. An ideal OER electrocatalyst should possess rich active sites and optimal binding strength with oxygen-containing intermediates. Although numerous endeavors have been devoted to the modification and optimization of transition-metal-based OER electrocatalysts, they are still operated with sluggish kinetics. Herein, an ion-exchange approach is proposed to realize the structure engineering of amorphous P–CoS hollow nanomaterials by utilizing the ZIF-67 nanocubes as the precursors. The precise structure control of the amorphous hollow nanostructure contributes to the large exposure of surface active sites. Moreover, the introduction of phosphorus greatly modifies the electronic structure of CoS₂, which is thus favorable for optimizing the binding energies of oxygenated species. Furthermore, the incorporation of phosphorus may also induce the formation of surface defects to regulate the local electronic structure and surface environment. As a result of this, such P–CoS hollow nanocatalysts display remarkable electrocatalytic activity and durability towards OER, which require an overpotential of 283 mV to afford a current density of 10 mA cm^?2, outperforming commercial RuO₂ catalyst.     

Revealing the role of Ni2+ ions in inducing the synthesis of porous carbon balls: A novel substrate to enhance the Pt catalytic activity towards methanol-oxidation

Carbon-based materials have been often employed as electrocatalytic substrates because of their large surface area/highly porous structure. Similar to carbon substrates, the non-carbon related materials such as transition metals also play an important role in improving catalytic performance. However, the simultaneous synthesis and metallic functionalization of carbon substrates is a highly challenging issue. Herein, a hydrothermal method has been used for the preparation of Ni-functionalized porous carbon balls. The significant role of Ni²⁺ ions in the synthesis of porous carbon balls has been confirmed. The results of transmission electron microscopy indicate that, the as-prepared porous carbon balls were suitable for the dispersion of Pt nanoparticles with small particle size (less than 4 nm). In addition to providing the OH_ads species, the Ni can also modify the surface electronic structure of Pt. Electrochemical measurements results reveal that, under the strong interactions between Ni and Pt, the as-prepared porous carbon balls supported Pt nanoparticles (Pt/Ni-CB) catalyst possesses excellent electrocatalytic activity, stability and CO anti-poisoning capability towards methanol electrooxidation reaction (MOR). This work opens a novel idea for the construction of the metal functionalization of carbon substrates and their subsequent applications in other electrocatalytic reactions.     

Facile fabrication of MOF-decorated nickel iron foam for highly efficient oxygen evolution

Metal-organic frameworks (MOFs) have emerged as efficient electrocatalysts due to the features of high specific surface area, rich pore structure and diversified composition. It is still challenging to synthesize self-supporting MOF-based catalysts using simple and low-cost fabrication methods. Herein, we successfully fabricated Ni-doped MIL-53(Fe) supported on nickel-iron foam (Ni-MIL-53(Fe)/NFF) as efficient electrocatalyst. A facile two-step solvothermal method without adding any metal salts was used, which can simplify the fabrication process and reduce the experimental cost. In the fabrication process, the bimetallic Ni-MIL-53(Fe)/NFF was in situ converted from an intermediate NiFe₂O₄/NFF. The obtained material exhibits outstanding electrocatalytic oxygen evolution performance with a low overpotential of 248 mV at 50 mA cm^?2, and a small Tafel slope of 46.4 mV dec^?1. This work sheds light on the simple and efficient preparation of bimetallic MOF-based material, which is promising in electrocatalysts.     

Spinel CoFe2O4 /carbon nanotube composites as efficient bifunctional electrocatalysts for oxygen reduction and oxygen evolution reaction

In the development of fuel cells, it is the key to large-scale commercialization of fuel cells to rationally design and synthesize efficient and non-noble metals-based bifunctional electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). In this paper, spinel CoFe₂O₄/carbon nanotube composites (CoFe₂O₄/CNTs/FA) were synthesized by solvothermal and calcination method. XRD, TEM, XPS and BET characterizations indicate that the addition of complexing agent fumaric acid can improve the crystal growth kinetics and morphology of CoFe₂O₄/CNTs nanohybirds. The as-synthesized CoFe₂O₄/CNTs/FA pyrolyzed at 500 °C have an outstanding bifunctional catalytic activity for ORR and OER with the potential of 1.62V (vs. RHE) at a current density of 10 mA/cm² and half-wave potential E_1/2 = 0.808V (vs. RHE) in alkaline electrolyte, respectively. It is obviously better than unloaded CoFe₂O₄ nanoparticles and commercial CNTs. CoFe₂O₄/CNTs/FA also exhibit better methanol tolerance ability and durability than commercial Pt/C and RuO₂ catalyst. This investigation broadens an idea of simple compounding of spinel with carbon-based materials to improve electrochemical properties.     

Astragali Radix-derived nitrogen-doped porous carbon: An efficient electrocatalyst for the oxygen reduction reaction

The development of biomass-derived nitrogen-doped porous carbons (NPCs) for the oxygen reduction reaction (ORR) is important for sustainable energy systems. Herein, NPCs derived from Astragali Radix (AR) via a cost-effective strategy are reported for the first time. The as-prepared AR-950-5 catalyst shows a stacked layer-like structure and porosity. Notably, the optimized AR-950-5 delivers catalytic activity comparable to that of commercial Pt/C (C-Pt/C), with high onset potential, positive half-wave potential and large limiting current density. It also displays superior long-term stability and methanol tolerance for ORR. This work will pave the way for a new approach in the development of highly active and low-cost NPCs for fuel cells.     

One-step synthesis of graphene supported platinum nanoparticles as electrocatalyst for PEM fuel cells

Here in, we describe an ultrafast, single-step microwave irradiation route (MW) to prepare graphene supported Pt nanoparticles, during which the small Pt nanoparticles are distributed uniformly on a reduced graphene oxide surface. This route provides evident advantages namely low cost, easiness, low time consuming and high yield in comparison to actual chemical methods to develop efficient Pt/rGO catalyst with Pt content close to state-of-the-art commercial composition. The structure and composition of prepared samples have been studied by specific techniques, while the electrocatalytic stability has been studied using ex-situ and in-situ measurements. High performance and electrochemically stable catalyst for PEM fuel cells was developed using the sample with highest loading and good dispersion. The fabricated Pt-rGO-based MEA was investigated for durability under fuel starvation in comparison with commercial Pt/C-based MEA. The electrocatalytic activity was investigated and the electrochemical response revealed the higher stability during accelerated degradation test under fuel starvation in comparison with commercial Pt/C. This study promotes the applicability of described preparation method to noble or transition metal nanoparticles embedded on graphene-based materials.     

Hexagonal CoFe2O4/β-Ni(OH)2 heterojunction composite as an advanced electrocatalyst for the oxygen evolution reaction

Transition metal-based heterostructure materials are considered as promising alternatives to state-of-the-art noble metal-based catalysts toward the oxygen evolution reaction (OER). Herein, for the first time, a simple interface engineering strategy is presented to synthesize efficient electrocatalysts based on a novel CoFe₂O₄/β-Ni(OH)₂ heterogeneous structure for the electrochemical OER. Remarkably, the optimized CoFe₂O₄/β-Ni(OH)₂ electrocatalyst, benefiting from its hierarchical hexagonal heterostructure with strong electronic interaction, enhanced intrinsic activity, and electrochemically active sites, exhibits outstanding OER electrocatalytic performance with a low overpotential of 278 mV to reach a current density of 10 mA cm⁻², a small Tafel slope of 67 mV dec⁻¹, and long-standing durability for 30 h. Its exceptional OER performance makes the CoFe₂O₄/β-Ni(OH)₂ heterostructure a prospective candidate for water oxidation in alkaline solution. The proposed interface engineering provides new insights into the fabrication of high-performance electrocatalysts for energy-related applications.     

Highly dispersed MnO nanoparticles supported on N-doped rGO as an efficient oxygen reduction electrocatalyst via high-temperature pyrolysis

Transition metal-based compounds, due to their excellent ORR catalytic performance under alkaline condition, have recently emerged as one of the most promising alternatives to noble metal-based ORR catalysts. It is worth noting that manganese oxide can take an unique advantage for decomposition of intermediate adsorption products H₂O₂ and can effectively reduce O₂ to OH⁻. However, most research has focused on MnO₂, while attention has rarely been paid to MnO catalysts. In addition, under high-temperature pyrolysis condition, MnO is the most stable manganese oxide but MnO nanoparticles easily agglomerate. Hence, it is very difficult to obtain well-dispersed and small-sized MnO nanoparticles. Herein, on the basis of pre-synthesizing uniformly distributed manganese complexes on the reduced graphene oxide (rGO), we innovatively prepare highly dispersed and small-sized MnO nanoparticles (~3.94 nm) via high-temperature pyrolysis, which are uniformly anchored on N-doped reduced graphene oxide (NrGO) as an efficient oxygen reduction electrocatalyst. The as-obtained MnO/NrGO (1050 °C) electrocatalyst achieves satisfactory onset potential (0.942 V) and half-wave potential (0.820 V) under alkaline condition. And the limiting current density is 4.17 mA cm⁻², which is very close to that of Pt/C (20 wt%, JM). Meanwhile, MnO/NrGO (1050 °C) catalyst presents superior longstanding durability and methanol resistance than Pt/C (JM). This work indicates that high-temperature pyrolysis can improve the purity of manganese oxide, simultaneously the defects of NrGO can reduce particle size of MnO nanoparticles, which are greatly beneficial to improve ORR performance. This work provides a new idea for research of MnO catalysts for ORR in the future.