Ultrafine CoRu alloy nanoclusters densely anchored on Nitrogen-Doped graphene nanotubes for a highly efficient hydrogen evolution reaction.

Designing highly efficient and stable electrocatalysts for hydrogen evolution reactions (HER) is essential to the production of green and renewable hydrogen. Metal-organic framework (MOF) precursor strategies are promising for the design of excellent electrocatalysts because of their porous architectures and adjustable compositions. In this study, a hydrogen-bonded organic framework (HOF) nanowire was developed as a precursor and template for the controllable and scalable synthesis of CoRu-MOF nanotubes. After calcination in Ar, the CoRu-MOF nanotubes were converted into N-doped graphene (NG) nanotubes with ultrafine CoRu nanoclusters (hereon called Co-xRu@NG-T; x  = 0, 5, 10, 15, 25 representing the Ru content of 0-0.25 mmol; T = 400 °C to 700 °C) that were densely encapsulated and isolated on the shell. Taking advantage of the synergistic effects of the porous, one-dimensional hollow structure and ultrafine CoRu nanoclusters, the optimized Co-15Ru@NG-500 catalyst demonstrated superior catalytic performance for HERs in alkaline electrolytes with an overpotential of only 30 mV at 10 mA cm-2 and robust durability for 2000 cycles, which outperforms many typical catalytic materials, such as commercial Pt/C. This work introduces a novel high-efficiency and cost-effective HER catalyst for application in commercial water-splitting electrolysis.

Enhancing oxygen evolution reactions in nanoporous high-entropy catalysts using boron and phosphorus additives.

High-entropy alloy (HEA) catalysts are a novel area of research in catalysis that shows great potential for more efficient catalyst development. Recent studies have highlighted the promise of HEA catalysts in applications such as water-splitting electrodes, owing to their better stability and ability to improve catalytic activity compared to traditional catalysts. Dealloying, which is a process that removes elements from metallic alloys, is a popular method for creating nanoporous HEA catalysts with large surface areas and interconnected structures. This study focused on the fabrication of nanoporous HEA catalysts with boron and phosphorus additives for the oxygen evolution reaction (OER) in water splitting. Combining B or P with noble metals such as Ir or Ru enhances the OER activity and durability, showing synergistic interactions between metals and light elements. This study used electrochemical evaluations to determine the best-performing catalyst, identifying CoCuFeMoNiIrB as the best catalyst for OERs in alkaline media. X-ray photoemission spectroscopy (XPS) analysis revealed that B effectively shifted the transition elements to higher valence states and induced excess electrons on the Ir-B surface to promote OER catalysis.

Selective Etching of Metal-Organic Frameworks for Open Porous Structures: Mass-Efficient Catalysts with Enhanced Oxygen Reduction Reaction for Fuel Cells.

Fe-Nx-C-based single-atom (SA-Fe-N-C) catalysts have shown favorable oxygen reduction reaction (ORR) activity. However, their application in proton exchange membrane fuel cells is hindered by reduced performance owing to the thick catalyst layer, restricting mass transfer and the O2 supply. Metal-organic frameworks (MOFs) are a promising class of crystal materials, but their narrow pores exacerbate the sluggish mass-transport properties within the catalyst layer. This study developed an approach for constructing an open-pore structure in MOFs via chelation-assisted selective etching, resulting in atomically dispersed Fe atoms anchored on an N, S co-doped carbon framework. The open-pore structure reduces oxygen transport resistance in the membrane electrode assembly (MEA) with unprecedented ORR activity and stability, as evidenced by finite element simulations. In an acidic electrolyte, the OP-Fe-NC catalyst shows a half-wave potential of 0.89 V vs RHE, surpassing Pt/C by 20 mV, and a current density of 29 mA cm-2 at 0.9 ViR-free in the MEA. This study provides an effective structural strategy for fabricating electrocatalysts with high mass efficiency and atomic precision for energy storage and conversion devices.

General Synthesis of MOF Nanotubes via Hydrogen-Bonded Organic Frameworks toward Efficient Hydrogen Evolution Electrocatalysts.

The application scope of metal-organic frameworks (MOFs) can be extended by rationally designing the architecture and components of MOFs, which can be achieved via a metal-containing solid templated strategy. However, this strategy suffers from low efficiency and provides only one specific MOF from one template. Herein, we present a versatile templated strategy in which organic ligands are weaved into hydrogen-bonded organic frameworks (HOFs) for the controllable and scalable synthesis of MOF nanotubes. HOF nanowires assembled from benzene-1,3,5-tricarboxylic acid and melamine via a simple sonochemical approach serve as both the template and precursor to produce MOF nanotubes with varied metal compositions. Hybrid nanotubes containing nanometal crystals and N-doped graphene prepared through a carbonization process show that the optimized NiRuIr alloy@NG nanotube exhibits excellent electrocatalytic HER activity and durability in alkaline media, outperforming most reported catalysts. The strategy proposed here demonstrates a pioneering study of combination of HOF and MOF, which shows great potential in the design of other nanosized MOFs with various architectures and compositions for potential applications.

Synthesis of Pyrochlore Oxides Containing Ir and Ru for Efficient Oxygen Evolution Reaction.

A versatile synthesis method for pyrochlore oxides containing Ir and Ru with lanthanides Pr, Nd, Eu, Gd, Tb, and Ho is herein presented. Based on the systematic synthesis and Rietveld refinement results, the lattice constants were tunable depending on the ionic radius of the lanthanide used. Subsequently, Pr-based pyrochlore oxides containing Ru and Ir in different ratios were fabricated for the oxygen evolution reaction (OER) in alkaline media, and the OER activity of these catalysts increased when the content of Ir and Ru was the same. Thus, the co-substitution of Ir and Ru in pyrochlore oxides is a novel synthesis strategy for electrocatalysts, which provides great potential for the fabrication of other pyrochlore oxides with various architectures and compositions for application in electrocatalysis.

Nanoporous ultra-high-entropy alloys containing fourteen elements for water splitting electrocatalysis.

High-entropy alloys (HEAs) are near-equimolar alloys comprising five or more elements. In recent years, catalysis using HEAs has attracted considerable attention across various fields. Herein, we demonstrate the facile synthesis of nanoporous ultra-high-entropy alloys (np-UHEAs) with hierarchical porosity via dealloying. These np-UHEAs contain up to 14 elements, namely, Al, Ag, Au, Co, Cu, Fe, Ir, Mo, Ni, Pd, Pt, Rh, Ru, and Ti. Furthermore, they exhibit high catalytic activities and electrochemical stabilities in the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in acidic media, superior to that of commercial Pt/graphene and IrO2 catalysts. Our results offer valuable insights for the selection of elements as catalysts for various applications.

Tailored Catalytic Nanoframes from Metal-Organic Frameworks by Anisotropic Surface Modification and Etching for the Hydrogen Evolution Reaction.

A facile anisotropic surface modification and etching strategy is presented for the synthesis of hollow structured ZIF-67 nanoframes. The strategy uses structural and compositional distinctions between each crystallographic facet of truncated rhombic dodecahedrons ZIF-67 (tZIF-67 RDs) and the moderate coordinating and etching effects of cyanuric acid (CA). The CA can anisotropically modify and protect the {110} facets from etching, causing the six {100} facets be selectively etched via an inside-out manner, and finally forming the hollow nanoframes. The surface-modified hollow tZIF-67 RDs can be facet-selectively etched by metal salts in an outside-in manner to give metal-doped tZIF-67 nanoframes. After calcination, the metal-tZIF-67 hybrids are converted into metal-Co alloy/C composite catalysts with hollow nanoframed structures. The PtCo/C catalyst with only 5.9 wt % Pt exhibits high catalytic activities and stabilities in the hydrogen evolution reaction (HER) in acidic solutions.

Magnetic-Electrospinning Synthesis of γ-Fe2O3 Nanoparticle-Embedded Flexible Nanofibrous Films for Electromagnetic Shielding.

The exploration of a new family of flexible and high-performance electromagnetic shielding materials is of great significance to the next generation of intelligent electronic products. In this paper, we report a simple magnetic-electrospinning (MES) method for the preparation of a magnetic flexible film, γ-Fe2O3 nanoparticle-embedded polymeric nanofibers. By introducing the extra magnetic field force on γ-Fe2O3 nanoparticles within composite fibers, the critical voltage for spinning has been reduced, along with decreased fiber diameters. The MES fibers showed increased strength for the magnetic field alignment of the micro magnets, and the attraction between them assisted the increase in fiber strength. The MES fibers show modifications of the magnetic properties and electrical conductivity, thus leading to better electromagnetic shielding performance.

Hierarchical Tubular Architecture Constructed by Vertically Aligned CoS2 -MoS2 Nanosheets for Hydrogen Evolution Electrocatalysis.

Developing efficient electrocatalysts for the hydrogen evolution reaction (HER) is crucial for establishing a sustainable and environmentally friendly energy system, but it is still a challenging issue. Herein, hierarchical tubular-structured CoS2 -MoS2 /C as efficient electrocatalysts are fabricated through a unique metal-organic framework (MOF) mediated self-sacrificial templating. Core-shell structured MoO3 @ZIF-67 nanorods are used both as a precursor and a sacrificial template to form the one-dimensional tubular heterostructure where vertically aligned two-dimensional CoS2 -MoS2 nanosheets are formed on the MOF-derived carbon tube. Trace amounts of noble metals (Pd, Rh, and Ru) are successfully introduced to enhance the electrocatalytic property of the CoS2 -MoS2 /C nanocomposites. The as-synthesized hierarchical tubular heterostructures exhibit excellent HER catalytic performance owing to the merits of the hierarchical hollow architecture with abundantly exposed edges and the uniformly dispersed active sites. Impressively, the optimal Pd-CoS2 -MoS2 /C-600 catalyst delivers a current density of 10 mA cm-2 at a low overpotential of 144 mV and a small Tafel slope of 59.9 mV/dec in 0.5 m H2 SO4 . Overall, this MOF-mediated strategy can be extended to the rational design and synthesis of other hollow heterogeneous catalysts for scalable hydrogen generation.

Hollow Functional Materials Derived from Metal-Organic Frameworks: Synthetic Strategies, Conversion Mechanisms, and Electrochemical Applications.

Hollow materials derived from metal-organic frameworks (MOFs), by virtue of their controllable configuration, composition, porosity, and specific surface area, have shown fascinating physicochemical properties and widespread applications, especially in electrochemical energy storage and conversion. Here, the recent advances in the controllable synthesis are discussed, mainly focusing on the conversion mechanisms from MOFs to hollow-structured materials. The synthetic strategies of MOF-derived hollow-structured materials are broadly sorted into two categories: the controllable synthesis of hollow MOFs and subsequent pyrolysis into functional materials, and the controllable conversion of solid MOFs with predesigned composition and morphology into hollow structures. Based on the formation processes of hollow MOFs and the conversion processes of solid MOFs, the synthetic strategies are further conceptually grouped into six categories: template-mediated assembly, stepped dissolution-regrowth, selective chemical etching, interfacial ion exchange, heterogeneous contraction, and self-catalytic pyrolysis. By analyzing and discussing 14 types of reaction processes in detail, a systematic mechanism of conversion from MOFs to hollow-structured materials is exhibited. Afterward, the applications of these hollow structures as electrode materials for lithium-ion batteries, hybrid supercapacitors, and electrocatalysis are presented. Finally, an outlook on the emergent challenges and future developments in terms of their controllable fabrications and electrochemical applications is further discussed.

Synthesis of Hollow Co-Fe Prussian Blue Analogue Cubes by using Silica Spheres as a Sacrificial Template.

Herein, we report a novel method for the formation of hollow Prussian blue analogue (CoFe-PBA) nanocubes, using spherical silica particles as sacrificial templates. In the first step, silica cores are coated by a CoFe-PBA shell and then removed by etching with hydrofluoric acid (HF). The cubic shape of CoFe-PBA is well-retained even after the removal of the silica cores, resulting in the formation of hollow CoFe-PBA cubes. The specific capacity of the hollow CoFe-PBA nanocubes electrodes is about two times higher than that of solid CoFe-PBA nanocubes as storage materials for sodium ions. Such an improvement in the electrochemical properties can be attributed to their hollow internal nanostructure. The hollow architecture can offer a larger interfacial area between the electrolyte and the electrode, leading to an improvement in the electrochemical activity. This strategy can be applied to develop PBAs with hollow interiors for a wide range of applications.