Efficient charge transfer has always been a challenge in heterogeneous MOF-based photoredox catalysis due to the poor electrical conductivity of the MOF photocatalyst, the toilless electron-hole recombination, and the uncontrollable host-guest interactions. Herein, a propeller-like tris(3'-carboxybiphenyl)amine () ligand was synthesized to fabricate a 3D ZnO cluster-based Zn(II)-MOF photocatalyst, Zn(TCBA)(μ-HO)HO (), which was applied to efficient photoreductive H evolution and photooxidative aerobic cross-dehydrogenation coupling reactions of -aryl-tetrahydroisoquinolines and nitromethane. In , the ingenious introduction of the meta-position benzene carboxylates on the triphenylamine motif not only promotes to exhibit a broad visible-light absorption with a maximum absorption edge of 480 nm but also causes special phenyl plane twists with dihedral angles of 27.8-45.8° through the coordination to Zn nodes. The semiconductor-like Zn clusters and the twisted antenna with multidimensional π interaction sites facilitate photoinduced electron transfer to render a good photocatalytic H evolution efficiency of 27.104 mmol·g·h in the presence of [Co(bpy)]Cl under visible-light illumination, surpassing many non-noble-metal MOF systems. Moreover, the positive enough excited-state potential of 2.03 V and the semiconductor-like characteristics of endow with double oxygen activation ability for photocatalytic oxidation of -aryl-tetrahydroisoquinoline substrates with a yield up to 98.7% over 6 h. The durability of and the possible catalytic mechanisms were also investigated by a series of experiments including PXRD, IR, EPR, and fluorescence analyses.
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http://dx.doi.org/10.1021/acs.inorgchem.3c00763 | DOI Listing |
Angew Chem Int Ed Engl
January 2025
Shanghai Institute of Organic Chemistry, Materials Science, 345 lingling Road, 200032, Shanghai, CHINA.
Three-dimensional covalent organic frameworks (3D COFs), a class of highly porous crystalline polymers, have exhibited great potentials in many applications. However, the reported topologies of 3D COFs have been limited to high-symmetry crystal systems, which significantly hindered the development of such functional materials. Herein, we demonstrate the first construction of four highly crystalline orthorhombic 3D COFs with an unprecedented fmj topology, based on judiciously choosing rotatable monomers.
View Article and Find Full Text PDFDalton Trans
January 2025
National Forestry and Grassland Administration Key Laboratory of Plant Fiber Functional Materials, College of Materials Engineering, Fujian Agriculture and Forestry University, Fuzhou 350002, China.
The unique benefits of nickel-aluminium layered double hydroxide (Ni-Al LDH)-based heterojunctions, including large surface area, tunable bandgap and morphology, abundant reaction sites, and high activity, selectivity, and photostability, make them extremely promising for photocatalytic applications. Given the importance and benefits of Ni-Al LDH-based heterojunctions in photocatalysis, it is necessary to provide a summary of Ni-Al LDH-based heterojunctions for photocatalytic applications. Hence, in this review, we thoroughly described the material design for Ni-Al LDH-based heterojunctions, along with their recent developments in various photocatalytic applications, , H evolution, CO reduction, and pollutant removal.
View Article and Find Full Text PDFNat Commun
January 2025
Tribology Research Institute, School of Mechanical Engineering, Southwest Jiaotong University, Chengdu, 610031, PR China.
Harvesting the energy from the interaction between hygroscopic materials and atmospheric water can generate green and clean energy. However, the ion diffusion process of moisture-induced dissociation leads to the disappearance of the ion concentration gradient gradually, and there is still a lack of moisture-based power generation devices with truly continuous operation, especially the duration of the current output still needs to be extended. Here, we propose a design for reconstructing the ion concentration gradient by coupling photocatalytic hydrogen evolution reaction with hydrovoltaic effect, to report a moisture-enabled electric generator (MEG) with continuous current output.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Tianjin University of Technology, Institute for New Energy Materials and Low Carbon Technologies, 300384, Tianjin, CHINA.
ACS Appl Mater Interfaces
January 2025
School of Chemistry and Pharmaceutical Science, Guangxi Normal University, Guilin 541004, China.
Imine-based covalent organic frameworks (COFs) have been widely applied in photocatalytic hydrogen peroxide (HO) production because of their highly crystalline properties and tunable chemical structures. However, the inherent polarization of C═N linkage brings a high energy barrier for π-electron delocalization, impeding the in-plane photoelectron transfer process, which leads to an inadequate efficiency of HO photosynthesis. In addition, the chemical stability of most imine-COFs remains insufficient due to the reversible nature of imine linkage.
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