Hollow Pd/MOF Nanosphere with Double Shells as Multifunctional Catalyst for Hydrogenation Reaction

A new type of hollow nanostructure featured double metal‐organic frameworks shells with metal nanoparticles (MNPs) is designed and fabricated by the methods of ship in a bottle and bottle around the ship. The nanostructure material, hereinafter denoted as Void@HKUST‐1/Pd@ZIF‐8, is confirmed by the analyses of photograph, transmission electron microscopy, scanning electron microscopy, powder X‐ray diffraction, inductively coupled plasma, and N₂ sorption. It possesses various multifunctionally structural characteristics such as hollow cavity which can improve mass transfer, the adjacent of the inner HKUST‐1 shell to the void which enables the matrix of the shell to host and well disperse MNPs, and an outer ZIF‐8 shell which acts as protective layer against the leaching of MNPs and a sieve to guarantee molecular‐size selectivity. This makes the material eligible candidates for the heterogeneous catalyst. As a proof of concept, the liquid‐phase hydrogenation of olefins with different molecular sizes as a model reaction is employed. It demonstrates the efficient catalytic activity and size‐selectivity of Void@HKUST‐1/Pd@ZIF‐8.     

Stimuli‐Responsive DNA‐Gated Nanoscale Porous Carbon Derived from ZIF‐8

Stimuli‐responsive nanoscale porous carbon derived from ZIF‐8 (NCZIF) gated by DNA capping units is reported. The NCZIF is first obtained by calcination of nano‐ZIF‐8 crystals under an inert atmosphere. It is further conjugated with amine‐modified single‐stranded DNA after carboxylation (DNA/NCZIF). The guest molecules are sealed in the pore of NCZIF by the formation of a DNA duplex structure on the surface of NCZIF. As proof of principle, two systems that can be, respectively, used for controlled drug delivery and biosensing are introduced. In the first system, the drug model (rhodamine 6G, Rh6G) is locked in the NCZIF by the DNA capping units composed of rich‐G sequences and its complementary DNA strand. The in vitro cellular experiments reveal that DNA/NCZIF has good biocompatibility and can controllably release Rh6G upon the K⁺‐stimuli in cells. In the second system, the signal probe (methylene blue, MB) is locked in the NCZIF and then released after the unlocking of the pores triggered by the dissociation of the aptamer‐hybrid capping units. The MB‐loaded DNA/NCZIF can linearly respond to target molecules in the range from 1 × 10^?9 to 10 × 10^?6 m and has good specificity.     

ZIF‐8@ZIF‐67‐Derived Nitrogen‐Doped Porous Carbon Confined CoP Polyhedron Targeting Superior Potassium‐Ion Storage

Potassium ion batteries (KIB) have become a compelling energy‐storage system owing to their cost effectiveness and the high abundance of potassium in comparison with lithium. However, its practical applications have been thwarted by a series of challenges, including marked volume expansion and sluggish reaction kinetics caused by the large radius of potassium ions. In line with this, the exploration of reliable anode materials affording high electrical conductivity, sufficient active sites, and structural robustness is the key. The synthesis of ZIF‐8@ZIF‐67 derived nitrogen‐doped porous carbon confined CoP polyhedron architectures (NC@CoP/NC) to function as innovative KIB anode materials is reported. Such composites enable an outstanding rate performance to harvest a capacity of ≈200 mAh g^?1 at 2000 mA g^?1. Additionally, a high cycling stability can be gained by maintaining a high capacity retention of 93% after 100 cycles at 100 mA g^?1. Furthermore, the potassium ion storage mechanism of the NC@CoP/NC anode is systematically probed through theoretical simulations and experimental characterization. This contribution may offer an innovative and feasible route of emerging anode design toward high performance KIBs.     

Co‐Induced Electronic Optimization of Hierarchical NiFe LDH for Oxygen Evolution

Developing efficient and stable non‐noble electrocatalysts for the oxygen evolution reaction (OER) remains challenging for practical applications. While nickel–iron layered double hydroxides (NiFe‐LDH) are emerging as prominent candidates with promising OER activity, their catalytic performance is still restricted by the limited active sites, poor conductivity and durability. Herein, hierarchical nickel–iron–cobalt LDH nanosheets/carbon fibers (NiFeCo‐LDH/CF) are synthesized through solvent‐thermal treatment of ZIF‐67/CF. Extended X‐ray adsorption fine structure analyses reveal that the Co substitution can stabilize the Fe local coordination environment and facilitate the π‐symmetry bonding orbital in NiFeCo‐LDH/CF, thus modifying the electronic structures. Coupling with the structural advantages, including the largely exposed active surface sites and facilitated charge transfer pathway ensured by CF, the resultant NiFeCo‐LDH/CF exhibits excellent OER activity with an overpotential of 249 mV at 10 mA cm^?1 as well as robust stability over 20 h.     

Shape‐Defined Hollow Structural Co‐MOF‐74 and Metal Nanoparticles@Co‐MOF‐74 Composite through a Transformation Strategy for Enhanced Photocatalysis Performance

In recent years, metal–organic frameworks (MOFs) have received extensive interest because of the diversity of their composition, structure, and function. To promote the MOFs' function and performance, the construction of hollow structural metal–organic frameworks and nanoparticle–MOF composites is significantly effective but remains a considerable challenge. In this article, a transformation strategy is developed to synthesize hollow structural Co‐MOF‐74 by solvothermal transformation of ZIF‐67. These Co‐MOF‐74 particles exhibit a double‐layer hollow shell structure without remarkable shape change compared to original ZIF‐67 particles. The formation of hollow structure stemmed from the density difference of Co between ZIF‐67 and Co‐MOF‐74. By this strategy, hollow structural Co‐MOF‐74 with different sizes and shapes are obtained from corresponding ZIF‐67, and metal nanoparticles@Co‐MOF‐74 is synthesized by corresponding nanoparticles@Co‐ZIF‐67. To verify the structural advantages of hollow structural Co‐MOF‐74 and Ag nanoparticles@Co‐MOF‐74, photocatalytic CO₂ reduction is used as a model reaction. Conventionally synthesized Co‐MOF‐74 (MOF‐74‐C), hollow structural Co‐MOF‐74 synthesized by transformation method (MOF‐74‐T) and Ag nanoparticles@Co‐MOF‐74 (AgNPs@MOF‐74) are used as cocatalysts in this reaction. As a result, the cocatalytic activity of MOF‐74‐T and AgNPs@MOF‐74 is 1.8 times and 3.8 times that of MOF‐74‐C, respectively.     

氮掺杂石墨烯原位生长碳纳米管复合过渡金属催化剂的制备及电催化性能EI北大核心CSCD

采用直接热解法,以石墨烯为载体,2-甲基咪唑锌盐MAF-4(ZIF8)为模板,尿素提供碳和氮源,Fe为过渡金属源,合成氮掺杂石墨烯(N/GO)和Fe-ZIF8(N-GO@Fe/ZIF8)的复合催化剂,并组装成锌空气电池。采用扫描电子显微镜(SEM)、透射电子显微镜(TEM)及电化学工作站等分析手段对催化剂的形貌、结构及电化学性能进行表征。结果表明:合成的N-GO@Fe/ZIF8-900催化剂具有优异的氧还原/氧析出(ORR/OER)性能。氧还原半波电位达到0.885 V,优于Pt/C(0.856 V),氧析出时,在10 mA/cm^(2)的电流密度下对应电位为1.811 V,优于贵金属Pt/C(1.968 V),与IrO_(2)(1.75 V)性能相当。组装成锌空气电池后,比能量和功率密度分别达到886.2 mW·h·g^(-1)和73.44 mW/cm^(2),高于贵金属Pt/C的比能量(791.04 mW·h·g^(-1))和功率密度(57.12 mW/cm^(2))。