Cu Promoted the Dynamic Evolution of Ni-Based Catalysts for Polyethylene Terephthalate Plastic Upcycling.

Upcycling plastic wastes into value-added chemicals is a promising approach to put end-of-life plastic wastes back into their ecocycle. As one of the polyesters that is used daily, polyethylene terephthalate (PET) plastic waste is employed here as the model substrate. Herein, a nickel (Ni)-based catalyst was prepared via electrochemically depositing copper (Cu) species on Ni foam (NiCu/NF).

Control over Charge Separation by Imine Structural Isomerization in Covalent Organic Frameworks with Implications on CO Photoreduction.

Two-dimensional covalent organic frameworks (COFs) are an emerging class of photocatalytic materials for solar energy conversion. In this work, we report a pair of structurally isomeric COFs with reversed imine bond directions, which leads to drastic differences in their physical properties, photophysical behaviors, and photocatalytic CO reduction performance after incorporating a Re(bpy)(CO)Cl molecular catalyst through bipyridyl units on the COF backbone (Re-COF). Using the combination of ultrafast spectroscopy and theory, we attributed these differences to the polarized nature of the imine bond that imparts a preferential direction to intramolecular charge transfer (ICT) upon photoexcitation, where the bipyridyl unit acts as an electron acceptor in the forward imine case (f-COF) and as an electron donor in the reverse imine case (r-COF).

Dominant Role of Hole Transport Pathway in Achieving Record High Photoconductivity in Two-Dimensional Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) with mobile charges have attracted significant attention due to their potential applications in photoelectric devices, chemical resistance sensors, and catalysis. However, fundamental understanding of the charge transport pathway within the framework and the key properties that determine the performance of conductive MOFs in photoelectric devices remain underexplored. Herein, we report the mechanisms of photoinduced charge transport and electron dynamics in the conductive 2D M-HHTP (M=Cu, Zn or Cu/Zn mixed; HHTP=2,3,6,7,10,11-hexahydroxytriphenylene) MOFs and their correlation with photoconductivity using the combination of time-resolved terahertz spectroscopy, optical transient absorption spectroscopy, X-ray transient absorption spectroscopy, and density functional theory (DFT) calculations.

Engineering Band Gap and Photoconduction in Semiconducting Metal Organic Frameworks: Metal Node Effect.

We report a systematic study on the correlation of the metal nodes in M-THQ conducting MOFs (M = Fe, Ni, Cu, and Zn; THQ = tetra-hydroxybenzoquinone) with their structure, photophysical property, and photoconductivity. We found that the structural preference in these MOFs is controlled by metal node identity where Cu prefers a square planar coordination which leads to a 2D Kagome-type structure. Fe, Ni, and Zn prefer an octahedral sphere which leads to a 3D structure.

Impact of π-Conjugation Length on the Excited-State Dynamics of Star-Shaped Carbazole-π-Triazine Organic Chromophores.

Correlating star-shaped donor-bridge-acceptor (DBA) molecular structures with intramolecular charge transfer (ICT) and intersystem crossing (ISC) is essential to their application in photocatalysis, photovoltaics, and organic light-emitting diodes (OLEDs). In this work, we report a systematic photophysical study on a series of star-shaped triazine-phenylene-carbazole DBA molecules with 0, 1, and 2 bridging phenylene units (pTCT-0P, pTCT-1P, pTCT-2P). Using a combination of steady-state and time-resolved spectroscopy with time-dependent density functional theory (TDDFT), we find that the bridge length can strongly impact the structural conformation, ICT, and ISC.

Tuning Photoexcited Charge Transfer in Imine-Linked Two-Dimensional Covalent Organic Frameworks.

The generation of a long-lived charge-separated state in versatile π-conjugated two-dimensional covalent organic frameworks (2D COFs), a process essential to extending their great potentials in advanced semiconducting applications, is yet fully elucidated. Herein, we report a systematic investigation of the photophysical properties of three highly crystalline imine-linked 2D COFs using steady-state and transient absorption spectroscopy accompanied by time-dependent density functional theory (TDDFT) calculations. The different electron affinity between 5,5',5″-(1,3,5-benzenetriyl)tris(2-pyridinecarboxaldehyde) (BTPA) and three tunable electron-donating/accepting triamine monomers dominated the formation of the excited-state, charge-transfer direction, and lifetime.

Conjugation- and Aggregation-Directed Design of Covalent Organic Frameworks as White-Light-Emitting Diodes.

2D covalent organic frameworks (COFs) have emerged as a promising class of organic luminescent materials due to their structural diversity, which allows the systematic tuning of organic building blocks to optimize emitting properties. However, a significant knowledge gap exists between the design strategy and the fundamental understanding of the key structural parameters that determine their photophysical properties. In this work, we report two highly emissive sp-C-COFs and the direct correlation of the structure (conjugation and aggregation) with their light absorption/emission, charge transfer (CT), and exciton dynamics, the key properties that determine their function as luminescent materials.

Direct Evidence of Photoinduced Charge Transport Mechanism in 2D Conductive Metal Organic Frameworks.

Conductive metal organic frameworks (MOFs) represent a promising class of porous crystalline materials that have demonstrated potential in photo-electronics and photocatalytic applications. However, the lack of fundamental understanding on charge transport (CT) mechanism as well as the correlation of CT mechanism with their structure hampered their further development. Herein, we report the direct evidence of CT mechanism in 2D Cu-THQ MOFs and the correlation of temporal and spatial behaviors of charge carriers with their photoconductivity by combining three advanced spectroscopic methods, including time resolved optical and X-ray absorption spectroscopy and terahertz spectroscopy.