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.     

Scalloped nickel/iron vanadium oxide-coated vanadium dioxides based on chemical etching-induced reconstruction strategy for efficient oxygen evolution

Developing highly efficient and stable noble metal-free electrocatalysts with excellent catalytic surface for oxygen evolution reactions (OER) is an essential link for stimulating hydrogen generation from water electrolysis. Herein, the scalloped nickel/iron vanadium oxide coated vanadium dioxide (named as VO₂@NFVO) has been successfully decorated via a urea-induced chemical etching-reconstruction process in the alkaline solution containing Fe²⁺ and Ni²⁺. Corresponding experimental measurements clearly show that favorable chemical etching occurs with the formation of new phases (eg, Ni₃V₂O₈, FeVO₄), which make it expose a large number of active sites and regulate the electron density of the active center, thus thereby dramatically enhancing the electrocatalytic performance by promoting electron transfer and optimizing the adsorption energy of reaction intermediates. Under optimized condition, the obtained VO₂@NFVO delivers excellent activity merely with smaller overpotential of 290 mV at 10 mA cm^?2, outperforming benchmark RuO₂ catalyst in an alkaline solution. Moreover, its superior durability is verified by chronoamperometry testing. This simple etching-reconstruction strategy opens a new avenue for the preparation of vanadium-based electrocatalysts.     

Petal-like NiCoP sheets on 3D nitrogen-doped carbon nanofiber network as a robust bifunctional electrocatalyst for water splitting

Searching high-active, stable and abundant bifunctional catalysts to replace noble metals for hydrogen and oxygen evolution reactions (HER and OER) is desired. Herein, petal-like NiCoP sheets were synthesized on carbon paper covered with a 3D nitrogen-doped carbon nanofiber network (NiCoP/CNNCP) by a simple hydrothermal process followed by phosphorization. The HER overpotential in 0.5 M H₂SO₄ and OER overpotential in 1 M KOH of the NiCoP/CNNCP electrode only required 55 mV and 260 mV to drive a current density of 10 mA cm^?2, respectively, which was comparable or even better than most nickel-and cobalt-based phosphide catalysts. The overall water-splitting electrolyzer with an asymmetric electrolyte system assembled using NiCoP/CNNCP as bifunctional electrodes required an extremely low cell voltage of 1.04 V to achieve a current density of 10 mA cm^?2, which was much lower than almost all alkaline electrolysis systems.     

Hydrogen-rich gas generation via the exhaust gas-fuel reformer for the marine LNG engine

Reformed exhaust gas recirculation technology has attracted great attention in internal combustion engines. A platform of an exhaust gas-fuel reformer connected with the marine LNG engine was set up for generating on-board hydrogen. Based on the platform, effects of the methane to oxygen ratio (M/O) and reformed exhaust gas ratio (R_EG) from the reformer and excess air ratio (λ) from the engine on the components, hydrogen yield, thermal efficiency and reforming process of the reformer were experimentally investigated. Results shown that hydrogen-rich gases (reformate) can be generated by reforming the mixture of engine exhaust gas (about 400 °C) and methane supplied via the reformer with Ni/Al₂O₃ catalyst, and the hydrogen concentration of reformate was between 6.2% and 12.6% by volume. The methane supplied rate and λ affected the components and temperature of the reactant in the reformer, while R_EG changed the gas hour space velocity during the exhaust gas-fuel reforming processes, resulting in the difference in the components of the reformate and thermal efficiency. At the present experimental condition, the highest H₂ concentration reformate was generated under the M/O of 2.0, λ of 1.55 and R_EG of 6%.     

Synthesis of hollow Fe,Co, and N-doped carbon catalysts from conducting polymer-metal-organic-frameworks core-shell particles for their application in an oxygen reduction reaction

Oxygen reduction reaction (ORR), one of the key reactions for fuel cells and zinc-air batteries, should be improved for higher performance. Herein, we fabricated hollow Fe, Co, and nitrogen co-doped carbon (H-FeCo-NC) catalyst, which was prepared by carbonization of core-shell particles made of polypyrrole (PPy)-coated polystyrene (PS) spheres as cores and (Zn, Co) bimetallic-zeolitic imidazolate frameworks (ZnCoBZIFs) as shells. PPy was used as a nitrogen and a carbon source. The H-FeCo-NC catalyst had a high surface area of 324.08 m² g^?1 with uniformly distributed Fe and Co species, and excellent ORR performance with the half-wave potential of 0.888 V vs. reversible hydrogen electrode in alkaline media. Furthermore, the H-FeCo-NC catalyst demonstrated exceptional stability, durability, and tolerance to methanol crossover.     

Morphological influence of graphitic carbon nanofibers by N–F dual-doping on Pt electrocatalytic activity and stability for oxygen reduction reaction in polymer electrolyte membrane fuel cells

Morphology of carbon nanofibers significantly effects Pt nanoparticles dispersion and specific interaction with the support, which is an important aspect in the fuel cell performance of the electrocatalysts. This study emphasizes, the defects creation and structural evolution comprised due to N–F co-doping on graphitic carbon nanofibers (GNFs) of different morphologies, viz. GNF-linearly aligned platelets (L), antlers (A), herringbone (H), and their specific interaction with Pt nanoparticle in enhancing the oxygen reduction reaction (ORR). GNFs–NF–Pt catalysts exhibit better ORR electrocatalytic activity, superior durability that is solely ascribed to the morphological evolution and the doped N–F heteroatoms, prompting the charge density variations in the resultant carbon fiber matrices. Amongst, H–NF–Pt catalyst performed outstanding ORR activity with exceptional electrochemical stability, which shows only 20 mV loss in the half-wave potential whilst 100 mV loss for Pt/C catalyst on 20,000 potential cycling. The PEMFC comprising H–NF–Pt as cathode catalyst with minimum loading of 0.10 mg cm^?2, delivers power density of 0.942 W cm^?2 at current density of 2.50 A cm^?2 without backpressures in H₂–O₂ feeds. The H–NF–Pt catalyst owing to its hierarchical architectures, performs well in PEMFC at the minimized catalyst loading with outstanding stability that can significantly decrease total price for the fuel cell.     

Ru-doped 3D porous Ni3N sphere as efficient Bi-functional electrocatalysts toward urea assisted water-splitting

Developing efficient, stable and ideal urea oxide (UOR) electrocatalyst is key to produce green hydrogen in an economical way. Herein, Ru doped three dimensional (3D) porous Ni₃N spheres, with tannic acid (TA) and urea as the carbon and nitrogen resources, is synthesized via hydrothermal and low-temperature treated process (Ru–Ni₃N@NC). The porous nanostructure of Ni₃N and the nickel foam provide abundant active sites and channel during catalytic process. Moreover, Ru doping and rich defects favor to boost the reaction kinetics by optimizing the adsorption/desorption or dissociation of intermediates and reactants. The above advantages enable Ru–Ni₃N@NC to have good bifunctional catalytic performance in alkaline media. Only 43 and 270 mV overpotentials are required for hydrogen evolution (HER) and oxygen evolution (OER) reactions to drive a current of 10 mA cm^?2. Moreover, it also showed good electrocatalytic performance in neutral and alkaline seawater electrolytes for HER with 134 mV to drive 10 mA cm^?2 and 83 mV to drive 100 mA cm^?2, respectively. Remarkably, the as-designed Ru–Ni₃N@NC also owns extraordinary catalytic activity and stability toward UOR. Moreover, using the synthesized Ru–Ni₃N@NC nanomaterial as the anode and cathode of urea assisted water decomposition, a small potential of 1.41 V was required to reach 10 mA cm^?2. It can also be powered by sustainable energy sources such as wind, solar and thermal energies. In order to make better use of the earth's abundant resources, this work provides a new way to develop multi-functional green electrocatalysts.     

Adjusting electronic structure coupling of Fe–Ni2P (NiFeP-MOF) multilevel structure for ultra-activity and durable catalytic water oxidation

Efficient electrocatalyst for alkaline oxygen evolution reaction is the critical core to the wide application of metal-air energy storage and water electrolysis hydrogen energy. Therefore, appropriate design of highly active and stable non-noble metal oxygen evolution electrocatalyst with good electronic structure and multilevel structure is both a goal and a challenge. Here, we report a Fe–Ni₂P electrocatalyst (NiFeP-MOF) with multilevel structure, which was obtained by anion exchange on the basis of Fe–Ni(OH)₂ (NiFe-MOF) grown on nickel foam in situ by solvothermal method. As expected, Fe substitution regulates the Ni oxidation state in the NiFeP-MOF and realizes electronic structure coupling, showing a highly active and stable oxygen evolution reaction (OER) in alkaline electrolyte solution. Specifically, the NiFeP-MOF demonstrates an ultralow overpotentials (232 mV, 10 mA cm^?2; 267 mV 100 mA cm^?2), respectively, an extremely small Tafel slope (34 mV dec^?1). Separately, the electrocatalyst shows an excellent cycle stability at 10 mA cm^?2 for 12 h (43,200 s). More importantly, this work come up with an available policy for the preparation of excellent alkaline hydrolysis electrolysis catalysts and air cathodes with excellent performance.     

Bifunctional nanoporous ruthenium-nickel alloy nanowire electrocatalysts towards oxygen/hydrogen evolution reaction

A class of ruthenium-nickel alloy catalysts featured with nanoporous nanowires (NPNWs) were synthesized by a strategy combining rapid solidification with two-step dealloying. RuNi NPNWs exhibit excellent electrocatalytic activity and stability for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in which the RuNi-2500 NPNWs catalyst shows an OER overpotential of 327 mV to deliver a current density of 10 mA cm^?2 and the RuNi-0 NPNWs catalyst requires the overpotential of 69 mV at 10 mA cm^?2 showing the best HER activity in alkaline media. Moreover, the RuNi-1500 NPNWs catalyst was used as the bifunctional electrocatalyst in a two-electrode alkaline electrolyzer for water splitting, which exhibits a low cell voltage of 1.553 V and a long-term stability of 24 h at 10 mA cm^?2, demonstrating that the RuNi NPNWs catalysts can be considered as promising bifunctional alkaline electrocatalysts.     

超高分子量聚乙烯纤维增强中空蜂窝模压复合材料性能研究

为研制车船等壳体所用的轻质、高强复合板材,选用超高分子量聚乙烯(UHMWPE)短纤维纱,制备成单层经纬为120根/(10 cm)的平纹组织,采用多组经纱持续更替交织层的方法制成2L(1+0)型、4L(2+1)型、6L(3+2)型3种多层角联锁结构织物,采用扦插芯棒、模压成型方法制成菱形蜂窝状的热固性环氧树脂基中空板,并与2块真空吸液法制成的面板组成“三合一”复合板,同时测定了复合板材的结构特征及其平拉、平压和弯曲性能。结果表明:3种类型复合板的密度均远小于水的密度,其中6L(3+2)型最小,为0.48 g/cm³;复合板层数越多,环氧树脂越难渗透尤其是在中空板菱形交叉点处,复合板平拉、平压、抗弯曲强度则呈现递增,制成的6L(3+2)型复合板试样平压强度可达到1.03 MPa。