Top-down preparation of Ni–Pd–P@graphitic carbon core-shell nanostructure as a non-Pt catalyst for enhanced electrocatalytic reactions

Electrochemical reactions such as the oxygen evolution reaction (OER), oxygen reduction reaction (ORR), and methanol oxidation reaction (MOR) are essential for energy conversion applications such as water electrolysis and fuel cells. Furthermore, Pt or Ir-related materials have been extensively utilized as electrocatalysts for the OER, ORR, and MOR. To reduce the utilization of precious metals, innovative catalyst structures should be proposed. Herein, we report a bi-metallic phosphide (Ni₂P and PdP₂) structure surrounded by graphitic carbon (Ni–Pd–P/C) with an enhanced electrochemical activity as compared to conventional electrocatalysts. Despite the low Pd content of 3 at%, Ni–Pd–P/C exhibits a low overpotential of 330 mV at 10 mA cm^?2 in the OER, high specific activity (2.82 mA cm^?2 at 0.8 V) for the ORR, and a high current density of 1.101 A mg^?1 for the MOR. The superior electrochemical performance of Ni–Pd–P/C may be attributed to the synergistic effect of the bi-metallic phosphide structure and core-shell structure formed by graphitic carbon.     

Iron-doped metal-organic framework with enhanced oxygen evolution reaction activity for overall water splitting

Water electrolysis is an energy conversion technology to provide green and clean hydrogen energy. Developing a high-efficient and durable electrocatalyst is a critical material for water electrolysis. Therefore, we synthesize a series of iron-doped metal-organic frameworks (MOFs) by a facile one-pot hydrothermal method. In the conventional three-electrode-cell, the Co/Fe (1:1)-MOF catalyst exhibits an overpotential of 317 mV at a current density of 10 mA cm⁻² in the oxygen evolution reaction (OER). Furthermore, the electrolysis performance of Co/Fe (1:1)-MOF catalyst is further evaluated in a home-made anion-exchange-membrane water electrolysis cell. With the Co/Fe (1:1)-MOF as the OER catalyst and commercial Pt/C as the hydrogen-evolution-reaction catalyst, the cell presents an overpotential of 490 mV at a large current density of 500 mA cm⁻², which is superior to the benchmark cell with commercial IrO₂ as the OER catalyst in the alkaline media. Theoretical calculation demonstrates that the introduction of Fe dopant into MOFs significantly reduces the binding energy of 1O and 1OOH intermedium during the OER progress. Consequently, the electrocatalytic activity is increased, which is perfectly consistent with the experimental results. This work suggests that the iron-doped MOFs structure significantly improves the electrocatalytic activity and provides a facile strategy to produce hydrogen at a large current density for industrial water electrolysis.     

Iron-doped cobalt nitride nanoparticles (Fe–Co3N): An efficient electrocatalyst for water oxidation

The exploration of efficient, low-cost and earth-abundant oxygen-evolution reaction (OER) electrocatalysts and the understanding of the intrinsic mechanism are important to advance the clean energy conversion technique based on electrochemical water oxidation. In this work, Fe-doping Co₃N catalysts were successfully synthesized by a simple nitridation reaction of the Co_3-xFe_xO₄ precursor. This material exhibited a low overpotential of 294 mV at a current density of 10 mA cm^?2, and a small Tafel slope of 49 mV dec^?1 in 1 M KOH solution, superior to the performance of Co₃N and IrO₂. As revealed by the spectroscopic and electrochemical analyses, the enhanced OER performance mainly originates from the electronic modulation induced by the incorporation of Fe into Co₃N, benefitting the formation of CoOOH as active surface species and thus facilitating the OER process. These findings also demonstrate the introduction of heterogeneous element is a simple and effective strategy to regulate the OER property of the cobalt nitrides (Co₃N) catalysts.     

Accelerating water dissociation kinetic in Co9S8 electrocatalyst by mn/N Co-doping toward efficient alkaline hydrogen evolution

Electrocatalytic hydrogen evolution under alkaline media holds great promising in hydrogen energy production. Transition-metal sulfides (TMSs) are attractive for electrocatalytic alkaline hydrogen evolution, yet their catalytic performance is unsatisfactory owing to the sluggish water dissociation kinetics. Herein, a Mn/N co-doping strategy is proposed to regulate the water dissociation kinetics of Co₉S₈ nanowires array grown on nickel foam thus improve the activity of hydrogen evolution reaction (HER). The optimal Mn/N co-doping Co₉S₈ (Mn–N–Co₉S₈) catalyst achieves low overpotentials of 102 and 238 mV at 10 and 100 mA cm^?2 in the 1 M KOH solution, respectively, remarkably higher than the single-doping Mn–Co₉S₈ and N–Co₉S₈ as well as superior to many reported Co₉S₈-based HER electrocatalysts. Density functional theory (DFT) calculation results confirm that the water dissociation barrier of the Mn–N–Co₉S₈ is reduced significantly owing to the synergistic co-doping of Mn and N, which accounts for the enhanced alkaline HER performance. This study offers an effective strategy to enhance the alkaline HER activity of TMSs by accelerating water dissociation kinetic via the cation and anion co-doping strategy.     

Metal organic frameworks as electrocatalysts: Hydrogen evolution reactions and overall water splitting

The development of clean energy technologies to protect the environment is an important demand of the times. Electrocatalysis is emerging as a promising method for evolution of hydrogen and overall water splitting. Nowadays, metal organic frameworks (MOFs) have emerged as electrocatalysts having uniformly distributed active sites and high electrical conductivity. This review summarizes the latest advances in heterogeneous catalysis by MOFs and their composite/derivatives for efficient hydrogen evolution reaction (HER) and water splitting. Pristine MOFs with their recent development are summarized first followed by composites of MOFs with their enhanced electrocatalytic performances. Overall water splitting by using bifunctional electrocatalysts derived from MOFs with different synthetic approaches is provided and this review gives the metal-based categorisation of precursor MOFs. Different strategies to improve chemical stability, conductivity, and overall electrocatalytic properties have been discussed. In the last, perspectives on the synthesis of efficient MOF-based electrocatalyst materials are provided.     

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.     

In-situ self-reconstruction of Ni–Fe–Al hybrid phosphides nanosheet arrays enables efficient oxygen evolution in alkaline

Developing efficient oxygen evolution reaction (OER) electrocatalysts with earth-abundant elements is very important for sustainable H₂ generation via electrochemical water splitting. Here we design a crystalline-amorphous Ni–Fe–Al hybrid phosphides nanosheet arrays grown on NiFe foam for efficient OER application. Dynamic surface reorganization of phosphides at anodic/cathodic polarizations is probed by in situ Raman spectroscopy. The reconstructed amorphous Ni(Fe)OOH species are determined as the active phases that facilitate the OER process. This unique electrode shows highly catalytic activity toward water oxidation, achieving the current densities of 10 and 100 mA cm^?2 at 181 and 214 mV in 1 M KOH, respectively. Meanwhile, it also exhibits excellent stability at a large current density of 100 mA cm^?2 for over 60 h. This work reveals the dynamic structural transformation of pre-catalyst in realistic conditions and highlights the important role of oxyhydroxides as real reactive species in OER process with high activity.     

Vanadium based zinc spinel oxides: Potential materials as photoanode for water oxidation and optoelectronic devices

In the recent past, layered zinc-based vanadium spinel oxides (ZnVOs) have shown an intriguing way to accomplish the challenges of energy conversion, storage, and utilization issues. Here, through first-principles calculations, a comprehensive study has been carried out to investigate the AV₂M (where A = Zn, Zn₂, Zn₃, Zn_4, and M = O₄, O₆, O₇, O₈, O₉ respectively) electronic, photocatalytic, and optical properties. Formation energies with a negative sign express that the final compounds from the pure elements are possible and cohesive energies revealed that compounds are energetically stable. Spin-polarized calculations are also taken into account for better approximation of the electronic properties (band structure and density of states). All layered structures show indirect bandgap for spin-up calculations in range 0.3 eV–2.4 eV, while spin-down calculations show mix trends in range 2.3 eV–3.50 eV. An appropriate band edge with large enough kinetic over-potentials of the oxygen evolution reaction (ΔE_V ≥ 1.244 eV) makes them potential candidates as photoanode for water splitting. ZnV₂O₄ is more suitable for OER as it has small kinetic overpotential as compared to the oxidation potential of water. Interestingly, all ZnVOs display a dramatically large coefficient (~10⁵ cm⁻¹) for optical absorption. Photogenerated electrons and holes on the layered zinc-based vanadium spinel oxide surfaces could make these spinel oxides promising materials for photocatalytic water splitting and solar energy conversion.     

Template confined construction of Fe–NiCoP/NiCoP/NF heterostructures for highly efficient electrocatalytic oxygen evolution reaction

Rational design of oxygen evolution reaction (OER) electrocatalysts with advance nanostructures and composition superiority is an urgent need to promote electrocatalytic property. In this research, we fabricate Fe–NiCoP/NiCoP/NF electrocatalyst for OER via the interfacial scaffolding strategy with Prussian-blue-analogue (PBA) followed by low-temperature phosphating. The cube-on-sheet multimetallic-TMPs-based nanoarchitecture of Fe–NiCoP/NiCoP/NF exhibits outstanding OER performance, which only requires the overpotential of 201 mV to achieve a current density of 10 mA cm⁻² and possesses good durability up to 50 h in 1.0 M KOH solution. The superior OER property of Fe–NiCoP/NiCoP/NF is mainly characteristic to the rich composition that optimizes the electronic structure and the cube-on-sheet multimetallic-TMPs-based nanoarchitecture which can facilitate more effective active sites exposure and ultimately promote charge transfer at the same time. This research provides a new strategy for the construction of advanced nanoarrays structure and the improvement of the electrocatalytic performance of polymetallic phosphides, which offers its promising applications especially in energy storage and conversion technology.     

Synthesis of CuTi-LDH supported on g-C3N4 for electrochemical and photoelectrochemical oxygen evolution reactions

A nanocomposite CuTi layered double hydroxide (LDH) supported on g-C₃N₄ (15 wt% of g-C₃N₄) is facilely synthesized by hydrothermal method. There are electrostatic interactions between positive layers of CuTi-LDH and negatively charged inner g-C₃N₄ sheets. The nanocomposite and its precursors are characterized through various analytical techniques, which affirmed the presence of both g-C₃N₄ and CuTi-LDH characteristic features. The pore-enriched hybrid geometry of CuTi-LDH@g-C₃N₄ with high specific surface area (146 m²/g), and suitable band gap of 2.46 eV enables the nanocomposite to act as both an electrocatalyst and photoelectrocatalyst for oxygen evolution reaction (OER). Both the electrochemical and photoelectrochemical studies are done using 1 M KOH (pH = 13.6) with applied potential of ?0.2 V to 1.5 V vs. Ag/AgCl. The onset potential of CuTi-LDH@g-C₃N₄ for OER appears at η = 0.36 V in dark and η = 0.32 V under visible light illumination of 30 min. Also, Mott-Schottky analysis shows n-type semiconductor behaviour for CuTi-LDH@g-C₃N₄ and its precursors. The photoelectrochemical water oxidation proceeds by charge transfer across a Type II heterojunction formed between the CuTi-LDH and g-C₃N₄ materials.