As the first example of a photocatalytic system for splitting water without additional cocatalysts and photosensitizers, the comparatively cost-effective Cu I -based MOF, Cu-I-bpy (bpy=4,4'-bipyridine) exhibited highly efficient photocatalytic hydrogen production (7.09 mmol g h ). Density functional theory (DFT) calculations established the electronic structures of Cu-I-bpy with a narrow band gap of 2.05 eV, indicating its semiconductive behavior, which is consistent with the experimental value of 2.00 eV. The proposed mechanism demonstrates that Cu I clusters of Cu-I-bpy serve as photoelectron generators to accelerate the copper(I) hydride interaction, providing redox reaction sites for hydrogen evolution. The highly stable cocatalyst-free and self-sensitized Cu-I-bpy provides new insights into the future design of cost-effective d -based MOFs for highly efficient and long-term solar fuels production.
The acid sites of zeolite are important local structures to control the products in the chemical conversion. However, it remains a great challenge to precisely design the structures of acid sites, since there are still lack the controllable methods to generate and identify them with a high resolution. Here, we use the lattice mismatch of the intergrown zeolite to enrich the inherent Lewis acid sites (LASs) at the interface of a mortise-tenon ZSM-5 catalyst (ZSM-5-MT) with a 90° intergrowth structure. ZSM-5-MT is formed by two perpendicular blocks that are atomically resolved by integrated differential phase contrast scanning transmission electron microscopy (iDPC-STEM). It can be revealed by various methods that novel framework-associated Al (AlFR) LASs are generated in ZSM-5-MT. Combining the iDPC-STEM results with other characterizations, we demonstrate that the partial missing of O atoms at interfaces results in the formation of inherent AlFR LASs in ZSM-5-MT. As a result, the ZSM-5-MT catalyst shows a higher selectivity of propylene and butene than the single-crystal ZSM-5 in the steady conversion of methanol. These results provide an efficient strategy to design the Lewis acidity in zeolite catalysts for tailored functions via interface engineering.
This work presents a cost-effective mixed-metal mixed-ligand MOF, which exhibits highly efficient photocatalytic H2 generation under visible-light irradiation.
A new [Co21(H2O)4(OH)12]30+ unit-incorporating polyoxotungstate (denoted as Co25Si6W60) has been hydrothermally synthesized and fully characterized. The unique Co25Si6W60-based biosensing system offers an environmentally-friendly route for detecting dichlorvos.
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