A metal–insulator–semiconductor (MIS) photosystem based on covalent organic framework (COF) semiconductors was designed for robust and efficient hydrogen evolution under visible‐light irradiation. A maximal H2 evolution rate of 8.42 mmol h−1 g−1 and a turnover frequency of 789.5 h−1 were achieved by using a MIS photosystem prepared by electrostatic self‐assembly of polyvinylpyrrolidone (PVP) insulator‐capped Pt nanoparticles (NPs) with the hydrophilic imine‐linked TP‐COFs having =C=O−H−N= hydrogen‐bonding groups. The hot π‐electrons in the photoexcited n‐type TP‐COF semiconductors can be efficiently extracted and tunneled to Pt NPs across an ultrathin PVP insulating layer to reduce protons to H2. Compared to the Schottky‐type counterparts, the COF‐based MIS photosystems give a 32‐fold‐enhanced carrier efficiency, attributed to the combined enhancement of photoexcitation rate, charge separation, and oxidation rate of holes accumulated in the valence band of the TP‐COF semiconductor.
Two-dimensional cobalt oxide (CoO) is a promising candidate for robust electrochemical capacitors with high performance. Herein, we use 2,3,5,6-tetramethyl-1,4-diisophthalate as a recyclable ligand to construct a Co-based metal-organic framework of UPC-9, and subsequently, we obtain ultrathin hierarchical CoO hexagonal nanosheets with a thickness of 3.5 nm through a hydrolysis and calcination process. A remarkable and excellent specific capacitance of 1121 F·g at a current density of 1 A·g and 873 F·g at a current density of 25 A·g were achieved for the as-prepared asymmetric supercapacitor, which can be attributed to the ultrathin 2D morphology and the rich macroporous and mesoporous structures of the ultrathin CoO nanosheets. This synthesis strategy is environmentally benign and economically viable due to the fact that the costly organic ligand molecules are recycled, reducing the materials cost as well as the environmental cost for the synthesis process.
A 3D non-interpenetrating porous metal-organic framework [Pb2(H2TCPP)]·4DMF·H2O (Pb-TCPP) (H6TCPP = 5,10,15,20-tetra(carboxyphenyl)porphyrin) was synthesized by employment of a robust porphyrin ligand. Pb-TCPP exhibits a one-dimensional channel possessing fairly good capability of gas sorption for N2, H2, Ar, and CO2 gases, and also features selectivity for CO2 over CH4 at 298 K. Furthermore, Pb-TCPP shows electrocatalytic activity for water oxidation in alkaline solution. It is the first 3D porous Pb-MOF that exhibits both gas adsorption properties and electrocatalytic activity for an oxygen evolution reaction (OER).
D‐π‐A type 4‐((9‐phenylcarbazol‐3‐yl)ethynyl)‐N‐dodecyl‐1,8‐naphthalimide (CZNI) with a large dipole moment of 8.49 D and A‐π‐A type bis[(4,4′‐1,8‐naphthalimide)‐N‐dodecyl]ethyne (NINI) with a negligible dipole moment of 0.28 D, were smartly designed and synthesized to demonstrate the evidence of a molecular dipole as the dominant mechanism for controlling charge separation of organic semiconductors. In aqueous solution, these two novel naphthalimides can self‐assemble to form nanoribbons (NRs) that present significantly different traces of exciton dissociation dynamics. Upon photoexcitation of NINI‐NRs, no charge‐separated excitons (CSEs) are formed due to the large exciton binding energy, accordingly there is no hydrogen evolution. On the contrary, in the photoexcited CZNI‐NRs, the initial bound Frenkel excitons are dissociated to long‐lived CSEs after undergoing ultrafast charge transfer within ca. 1.25 ps and charge separation within less than 5.0 ps. Finally, these free electrons were injected into Pt co‐catalysts for reducing protons to H2 at a rate of ca. 417 μmol h−1 g−1, correspondingly an apparent quantum efficiency of ca. 1.3 % can be achieved at 400 nm.
Well-defined Zn2GeO4 hexagonal nanorods and nanofibers with high aspect ratios have been readily realized in high yield via a simple and general hydrothermal synthesis method free of any surfactant or template. Field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectrometry (EDX), powder X-ray diffraction (XRD), and ultraviolet-visible light diffuse reflectance spectroscopy (UV-vis DRS) revealed a unique hexagonal-prism-shaped one-dimensional (1-D) structure, surface features, anisotropic crystal growth, and crystal phase of Zn2GeO4. Detailed investigations indicated that the prismatic Zn2GeO4 nanocrystals are uniform single crystal with the longitudinal direction along the [001] and were dominated by (110) and (110) surfaces. The addition of increasing amounts of NaOH was found to facilitate the morphology transition from a hexagonal nanorod shape to a hexagonal fiber shape. As an important wide-band-gap photocatalyst, the products of regular Zn2GeO4 nanocrystals with a hexagonal 1-D structure exhibit superior photocatalytic activities for the photocatalytic decomposition of water-methanol solution to hydrogen under UV irradiation.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.