RESUMEN
The hierarchical self-assembly of colloidal particles facilitates the bottom-up manufacturing of metamaterials with synergistically integrated functionalities. Here, we define a modular assembly methodology that enables multinary co-assembly of nanoparticles in one-dimensional confined space. A series of isotropic and anisotropic nanocrystals such as plasmonic, metallic, visible, and near-infrared responsive nanoparticles as well as transition-metal phosphides can be selectively assembled within the single-walled Co(OH)2 nanotubes to achieve various increasingly sophisticated assembly systems, including unary, binary, ternary, and quaternary superstructures. Moreover, the selective assembly of distinct functional nanoparticles produces different integrated functional superstructures. This generalizable methodology provides predictable pathways to complex architectures with structural programming and customization that are otherwise inaccessible.
RESUMEN
Exfoliation and interfacial modification of two-dimensional (2D) polymeric carbon nitride (CN) are considerably vital for applications in photo/electrocatalysis fields. Here, a grinding-ultrasonic route was designed to construct nickel bis(chelate) complex (Ni(abt)2, abt = 2-aminobenzenethiolate)-modified CN ultrathin nanosheets. Under the assistance of the shear force derived from the grinding process, Ni(abt)2 was implanted into the interlamination of bulk CN, resulting in the formation of ultrathin CN (UCN) nanosheets. Simultaneously, Ni(abt)2 molecules were anchored on the surfaces of as-formed UCN nanosheets due to the π-π stacking interaction. Interestingly, compared with single Ni(abt)2 and UCN, the as-obtained Ni(abt)2/UCN nanosheets exhibited excellent photocatalytic hydrogen evolution capability. A molecule-semiconductor internal electron transmission mechanism was suggested for explaining the separation and transfer of electron-hole pairs. Density functional theory (DFT) calculations demonstrated that the interface-induced electron redistribution tuned the electron density and hydrogen adsorption of the active centers, thus enhancing the photocatalytic performance of the hybrid catalyst. In addition, the as-obtained Ni(abt)2/UCN nanosheets could also catalyze the reduction of nitroaromatics in the presence of NaBH4. It was found that under the simulated sunlight irradiation, the conversion efficiency of nitroaromatic compounds to amino aromatic ones was up to 97.3%, far higher than that under the condition without light irradiation (51.7%), suggesting that the photocatalytic-produced hydrogen took part in the reduction of nitroaromatic compounds.
RESUMEN
Much effort has been devoted to improving the photocatalytic capacity of graphitic carbon nitride (g-C3N4). In this paper, we reported the successful synthesis of a hybrid photocatalyst with superb photocatalytic hydrogen production activity through decorating atomically precise Ni6(SC2H4Ph)12 nanoclusters on g-C3N4 nanosheets (labeled as Ni6/g-C3N4) at room temperature. Zeta potential experiments demonstrated that the electrostatic interaction between Ni6 and g-C3N4 led to the formation of Ni6/g-C3N4. The photocatalytic measurements revealed that the 5 %-Ni6/g-C3N4 prepared with the original mass ratio of m(Ni6)/m(g-C3N4) = 1/20 exhibited the strongest hydrogen production activity. In the system with triethanolamine (TEOA) as the sacrifice agent, the visible-light hydrogen production rate reached up to 5.87 mmol h-1 g-1, approximately 290 times higher than that of pure g-C3N4 (0.02 mmol h-1 g-1). Density functional theory (DFT) calculations testified that the above significant enhancement of photocatalytic hydrogen evolution of the hybrid photocatalyst arose from the photogenerated electrons transfer from Ni6 to g-C3N4.
RESUMEN
Novel tetranuclear organocopper(I) clusters bridged by two halides and two indolyl-based NCN pincer ligands were synthesized through the reactions of Cu(I) halides with lithiated ligands. Single-crystal X-ray diffraction revealed that the structure of these complexes included a [Cu4X2]2+ cluster unit wherein the four copper ions were stabilized by multiple Cu-Cu interactions, arranged in a distorted tetrahedral fashion and the halide anions µ3-bridged with metal centers. Meanwhile, these clusters displayed excellent catalytic activities towards the hydrophosphination of alkenes under solvent-free conditions with wide functional group tolerance.
