Hierarchical NiMoP2-Ni2P with amorphous interface as superior bifunctional electrocatalysts for overall water splitting

Producing highly efficient bifunctional catalyst for the generation of hydrogen and oxygen through overall water splitting is an emerging direction in electrocatalysis,Herein,a dandelion-like hierarchi-cal NiMoP2-Ni2P(nanowire/nanoparticle)heterostructure was synthesized for efficient electrochemical water splitting.The NiMoP2-Ni2P heterostructures grown on carbon cloth as a freestanding integrated electrode exhibited excellent oxygen evolution reaction(OER)activity and hydrogen evolution reaction(HER)activities with low overpotentials(258 mV and 53 mV to reach 10 mA cm-2 for the OER and HER,respectively),and small Tafel slope(45 mV dec-1 and 58 mV dec-1 for the OER and HER,respectively).Moreover,the NiMoP2-Ni2 P heterostructure can act as both anode and cathode catalysts for overall water splitting with low overall potential of 1.48 V at 10 mA cm-2.Density functional theory(DFT)combined with structural probes suggests that the amorphous heterogeneous interfaces play an essential role in enhanced catalytic performance.     

钴-镍双金属磷化物中空纳米笼用于高效电解水

制备一种低成本、高效、稳定耐用的双功能电催化剂对于电催化水分解至关重要.本文采用自模板策略和原位磷化工艺相结合的方法构建了一种具有中空结构的钴镍双金属磷化物纳米笼(CoNiP_(x)).由于其独特的中空结构和钴镍双金属之间的协同效应,合成的CoNiP_(x)中空纳米笼催化剂在全pH值范围的电解质中对析氢反应均表现出优异...     

Ternary NiCoP nanosheet arrays: An excellent bifunctional catalyst for alkaline overall water splitting

Exploring bifunctional catalysts for the hydrogen and oxygen evolution reactions (HER and OER) with high efficiency,low cost,and easy integration is extremely crucial for future renewable energy systems.Herein,ternary NiCoP nanosheet arrays (NSAs) were fabricated on 3D Ni foam by a facile hydrothermal method followed by phosphorization.These arrays serve as bifunctional alkaline catalysts,exhibiting excellent electrocatalytic performance and good working stability for both the HER and OER.The overpotentials of the NiCoP NSA electrode required to drive a current density of 50 mA/cm2 for the HER and OER are as low as 133 and 308 mV,respectively,which is ascribed to excellent intrinsic electrocatalytic activity,fast electron transport,and a unique superaerophobic structure.When NiCoP was integrated as both anodic and cathodic material,the electrolyzer required a potential as low as ～1.77 V to drive a current density of 50 mA/cm2 for overall water splitting,which is much smaller than a reported electrolyzer using the same kind of phosphide-based material and is even better than the combination of Pt/C and Ir/C,the best known noble metal-based electrodes.Combining satisfactory working stability and high activity,this NiCoP electrode paves the way for exploring overall water splitting catalysts.     

A co-coordination strategy to realize janus-type bimetallic phosphide as highly efficient and durable bifunctional catalyst for water splitting

In this work,a Janus-type dual-ligand metal-organic frameworks derived bimetallic (Fe,Co)P nanoparticles embedded carbon nanotube (CNT) skeleton (DLD-FeCoP@CNT) is presented and synthesized via a facile "co-coordination synthesis" strategy.The DLD-FeCoP@CNT hybrid shows much better performances for OER and HER with much lower Tafel slope of 39.6 (57.1) mV dec-1,an overpotential of 286 (166) mV@10 mA cm-2 and better stability for OER (HER) in 1 M KOH.Being both cathode and anode for water splitting,it requires only a low voltage of 1.67 V to obtain 10 mAcm-2 with nearly 100％ faradaic efficiency,which is close to Pt/C//RuO2 cell.Density functional theory calculations based on the bimetallic phosphide (Fe0.3Co0.7P) model reveal that,compared with the monometallic FeP or CoP,the enhanced catalytic activities of Fe0.3Co0.7P is mainly manifested in its free energy of H adsorption (△GH*) closer to zero,larger binding strength for H2O and higher electrical conductivity.     

Facile fabrication of three-dimensional interconnected nanoporous N-TiO2 for efficient photoelectrochemical water splitting

Three-dimensional (3D) interconnected porous architectures are expected to perform well in photoelectrochemical (PEC) water splitting due to their high specific surface area as well as favourable porous properties and interconnections. In this work, we demonstrated the facile fabrication of 3D interconnected nanoporous N-doped TiO₂ (N-TiO₂ network) by annealing the anodized 3D interconnected nanoporous TiO₂ (TiO₂ network) in ammonia atmosphere. The obtained N-TiO₂ network exhibited broadened light absorption, and abundant, interconnected pores for improving charge separation, which was supported by the reduced charge transfer resistance. With these merits, a remarkably high photocurrent density at 1.23 V vs. reversible hydrogen electrode (RHE) was realized for the N-TiO₂ network without any co-catalysts or sacrificial reagents, and the photostability can be assured after long term illumination. In view of its simplicity and efficiency, this structure promises for perspective PEC applications.     

Metal-organic framework derived hierarchical NiCo2O4 triangle nanosheet arrays@SiC nanowires network/carbon cloth for flexible hybrid supercapacitors

To overcome the disadvantages of traditional powder electrodes,such as the insufficient performance,the aggregation of active materials,and the complex fabrication process,rationally constructing free-standing electrode materials with hierarchical architecture is an effective and promising method,which could further improve the electrochemical properties.Herein,using metal-organic framework nanoar-rays (MOFNAs) as self-sacrificial templates and SiC nanowires (SiCNWs) network as nanoscale conductive skeletons,we successfully fabricated the hierarchical core-shell SiCNws@NiCo2O4NAs on carbon cloth (CC)substrate.Taking advantages of structural merits,such as hierarchical porous triangle-like NiCo2O4NAs,the interwoven SiCNWs network and conductive CC substrate,when evaluated as a binder-free superca-pacitor electrode,the CC/SiCNWs@NiCo2O4NAs shows a high specific capacitance of 1604.7 F g-1 (specific capacity of 222.9 mA h g-1) at 0.5 A g 1,good rate performance,and excellent cycling stability.Signifi-cantly,the hybrid supercapacitor assembled with CC/SiCNWs@NiCo2O4NAs as the cathode and MOF derived CC/SiCNWs@CNAs as the anode,could deliver a high specific density of 49.9 W h kg-1 at a specific power of 800 W kg-1,stable cycling performance,and good flexibility.Impressively,this feasible strategy for fabricating hierarchical structure displays great potential in the field of energy storage.     

Visible light active ZnIn2S4/g-C3N4 heterostructure nanocomposite photoelectrode for efficient photoelectrochemical water splitting activity

Hexagonal zinc indium sulfide coupled g-C₃N₄ (H-ZnIn₂S₄/g-C₃N₄) nanocomposites were synthesized using chemisorption method and its performance towards photoelectrochemical water splitting activity was studied. The H-ZnIn₂S₄/g-C₃N₄ (H-ZIS/CN) nanocomposites exhibited ∼ 1.9 times enhanced photoelectrochemical performance as compared to the H-ZnIn₂S₄. The enhancement in the PEC water splitting activity of H-ZIS/CN nanocomposite is ascribed to the formation of type-II heterojunction which resulted in improved separation of photogenerated charge carriers and faster transfer of charges at the photoelectrode/electrolyte interface. The electrochemical impedance study and Mott-Schottky supported these results. Moreover, during photoelectrochemical reactions, H-ZIS/CN nanocomposites showed tremendous stability under visible light. A potential mechanism of the enhanced photoelectrochemical activity of H-ZIS/CN nanocomposites was proposed and endorsed by the PEC results. This study demonstrates that establishing a heterostructure system by coupling a ternary chalcogenide semiconductor with a conducting polymer is an effective strategy for PEC water splitting applications.     

A bifunctional electrocatalyst of PtNi nanoparticles immobilized on three-dimensional carbon nanofiber mats for efficient and stable water splitting in both acid and basic media

Inspired by the excellent activity of platinum in hydrogen evolution reaction (HER) and the good performance of Ni-based compounds in oxygen evolution reaction (OER), a bifunctional electrocatalyst PtNi carbon nanofiber (CNF) is designed and fabricated using electrospinning followed by carbonization. Ultra-small PtNi nanoparticles of several nanometers in size are densely dispersed on every CNF, along with a few larger nanoparticles with sizes of several decades of nanometers. The as-prepared catalysts can be directly used as an electrode and act as high-efficiency materials for water splitting, including HER and OER. For HER activity, the PtNi/CNFs reach 10 mA cm^?2 current density at low overpotentials of 34 mV and exhibit a small Tafel slope of 31 mV dec^?1 in acidic electrolytes of 0.5 M H₂SO₄, which is close to that of commercial Pt/C (20 wt%) electrocatalytic catalysts. In 1 M KOH solution, the PtNi/CNFs also exhibit excellent HER activity with a low overpotential of 82 mV to achieve a current density of 10 mA cm^?2 and a small Tafel slope of 34 mV dec^?1. Moreover, the PtNi/CNFs also show good activity for OER in alkaline electrolyte of 1 M KOH with a Tafel slope of 159 mV dec^?1 and a small overpotential of 151 mV to reach a current density of 10 mA cm^?2. In addition, the OER performance of the PtNi/CNFs in acid media is also favorable, with a 198 mV dec^?1 Tafel slope. The decent activity of the PtNi/CNFs for water splitting originates from the synergistic effects of using Pt and Ni, large amounts of ultra-small nanoparticles densely dispersed on the CNFs, high conductivity of the support materials and interconnected three-dimensional structures of the carbon nanofiber mats.     

Monodispersed Pt Sites Supported on NiFe-LDH from Synchronous Anchoring and Reduction for High Efficiency Overall Water Splitting

Precise design of low-cost, efficient and definite electrocatalysts is the key to sustainable renewable energy. Herein, this work develops a targeted-anchored and subsequent spontaneous-redox strategy to synthesize nickel-iron layered double hydroxide (LDH) nanosheets anchored with monodispersed platinum (Pt) sites (Pt@LDH). Intermediate metal-organic frameworks (MOF)/LDH heterostructure not only provides numerous confine points to guarantee the stability of Pt sites, but also excites the spontaneous reduction for Pt^II. Electronic structure, charge transfer ability and reaction kinetics of Pt@LDH can be effectively facilitated by the monodispersed Pt moieties. As a result, the optimized Pt@LDH that with the 5% ultra-low content Pt exhibits the significant increment in electrochemical water splitting performance in alkaline media, which only afford low overpotentials of 58 mV at 10 mA cm⁻² for hydrogen evolution reaction (HER) and 239 mV at 10 mA cm⁻² for oxygen evolution reaction (OER), respectively. In a real device, Pt@LDH can drive an overall water-splitting at low cell voltage of 1.49 V at 10 mA cm⁻², which can be superior to most reported similar LDH-based catalysts. Moreover, the versatility of the method is extended to other MOF precursors and noble metals for the design of ultrathin LDH supported monodispersed noble metal electrocatalysts promoting research interest in material design.     

Pulse electrodeposition of Ag,Cu nanoparticles on TiO2 nanoring/nanotube arrays for enhanced photoelectrochemical water splitting

In this paper, plasmonic Ag and Cu nanoparticles were co-deposited on TiO₂ nanoring/nanotube arrays (TiO₂ R/T) by using two-step pulse electrodeposition method for investigating the optical and photoelectrochemical properties, in comparison to monometallic Ag, Cu decoration. By optimizing the electrodeposition cycle times and electrolyte concentration, bimetallic Ag–Cu/TiO₂ R/T-0.5 with moderate densities and sizes of Ag and Cu nanoparticles was fabricated and shows great photocatalytic potential, in which, Ag mainly facilitates the generation of hot electrons by absorbing visible light and Cu plays an important role in accelerating the separation and transportation of hot electrons. The hydrogen production rate was tested as 425 μL h^?1 cm^?2, which is about 1.34-fold enhanced H₂ production over TiO₂ R/T. Furthermore, molecular dynamics simulations were made for analyzing the interface electrostatic properties between plasmonic nanoparticles of Ag or Cu and the semiconductor TiO₂. It is calculated that bimetallic Ag–Cu/TiO₂/H₂O system has larger interfacial Helmholtz potential than monometallic Ag/TiO₂/H₂O, Cu/TiO₂/H₂O and pure TiO₂/H₂O systems, accelerating the four-electron reaction occurring at the semiconductor/electrolyte interface. This research put forward a feasible and simple pulse electrodeposition method to fabricate bimetallic photoanodes for enhanced hydrogen evolution and an important analysis method of semiconductor/ metal/electrolyte interface characteristics.     

Quaternary pyrite-structured nickel/cobalt phosphosulfide nanowires on carbon cloth as efficient and robust electrodes for water electrolysis

The strategy of element substitution is an effective way to tune the electronic structures of the active sites in catalysts,thereby leading to improvements in both the catalytic activity and stability.Herein,we design and synthesize pyrite-type nickel/phosphorus co-doped CoS2 nanowires on carbon cloth (NiCoPS/CC) as efficient and durable electrodes for water electrolysis.Introduction of nickel and phosphorus produced stepwise and superb enhancement of the performance of the electrodes in the hydrogen evolution reaction due to regulation of the electronic structures of the active sites of the catalyst and accelerated charge transfer over a wide pH range (0-14).The NiCoPS/CC electrodes also delivered a nearly undecayed catalytic current density of 10 mA.cm-2 at a low overpotential of 230 mV for oxygen evolution due to in situ formation of surficial Ni-Co oxo/hydroxide in 1.0 M KOH.Thus,the NiCoPS/CC electrodes gave rise to a catalytic current density of 10 mA.cm-2 for overall water splitting at potentials as low as 1.54 V during operation over 100 h in 1.0 M KOH with a Faradic efficiency of ～100％.