Chemically Bonded Plasmonic Triazole‐Functionalized Au/Zeolitic Imidazole Framework (ZIF‐67) for Enhanced CO₂ Photoreduction

Abstract

The design of functionalized metallic nanoparticles is considered an emerging technique to ensure the interaction between metal and semiconductor material. In the literature, this interface interaction is mainly governed by electrostatic or van der Waals forces, limiting the injection of electrons under light irradiation. To enhance the transfer of electrons between two compounds, close contact or chemical bonding at the interface is required. Herein, a new approach was reported for the synthesis of chemically bonded plasmonic Au NPs/ZIF-67 nanocomposites. The structure of ZIF-67 was grown on the surface of functionalized plasmonic Au NPs using 1H-1,2,4-triazole-3thiol as the capping agent, which acted as both stabilizer of Au nanoparticles and a molecular linker for ZIF-67 formation. As a result, the synthesized material exhibited outstanding photocatalytic CO 2 reduction with a methanol production rate of 2.70 mmol h À 1 g À 1 cat under sunlight irradiation. This work emphasizes that the diligent use of capping agents, with suitable functional groups, could facilitate the formation of intimate heterostructure for enhanced photocatalytic CO 2 reduction.

In‐situ Integrated Plasmonic TiN@ZIF‐67 Composites for the Photoreduction of CO2into Solar Fuels: Insights into their Plasmonic Interaction and Mechanism

“…The crystalline properties of the synthesized TiN/PVP‐ZIF and TiN/ImCHO‐ZIF composites were characterized using X‐ray diffraction (XRD) analysis and the results are shown in Figure 3. As observed, the bare‐ZIF‐67 (line a) exhibits the characteristic diffraction peaks at 2θ=12.7° and 16.5° corresponding to the diffraction plane (112) and (013) [17,29,39] . Besides, all the characteristic peaks of ZIF‐67 can be seen in the composites TiN/PVP‐ZIF (line b) and TiN/ImCHO‐ZIF (line c), which indicate that both the plasmon‐based composites have been successfully synthesized.…”

“…As observed, the bare-ZIF-67 (line a) exhibits the characteristic diffraction peaks at 2θ = 12.7°and 16.5°corresponding to the diffraction plane (112) and ( 013). [17,29,39] Besides, all the characteristic peaks of ZIF-67 can be seen in the composites TiN/PVP-ZIF (line b) and TiN/ImCHO-ZIF (line c), which indicate that both the plasmon-based composites have been successfully synthesized. In addition, a weak peak in 2θ = 40°is observed, which can be assigned to the crystal facet (200) of Ti.…”

“…The as‐synthesized material showed a total of 3.2 mmol g −1 h −1 of CH 3 OH generation, which is one of the promising values considering the challenges in the field. This observed catalytic performance was attributed to the plasmonic effect leading to a rapid injection of electrons and their rich availability to reduce CO 2 [17] …”

“…This observed catalytic performance was attributed to the plasmonic effect leading to a rapid injection of electrons and their rich availability to reduce CO 2 . [17] Nevertheless, despite the high catalytic performance of Au plasmon-based materials, their economic feasibility is still a big challenge for industrial scale-up. [18] Alternatively, in recent years, plasmonic titanium nitride (TiN) offers a cost-effective solution to potentially replace conventional plasmonic materials such as gold and silver.…”

Au Nanoparticle-Anchored Hollow Nanospheres of a Single-Atomized Porphyrin-Covalent Organic Framework Hybrid for Boosting Photoreduction of CO2 under Solar Irradiation

“…When light is shone on a sample of Au nanoparticles, the electrons within them are free to conduct the electricity, creating a resonance with the incident light’s electromagnetic field. Thus, the hot electrons with surplus energy that are triggered by LSPR can either go to the adjacent absorbent or return to the ground state by dissipating the energy to the environment. − When these factors are taken into account, it becomes effective to construct COF photocatalyst systems that integrate plasmonic Au nanoparticles toward CO 2 reduction.…”