Rhenium(I) Complex-Containing Amphiphilic Metallopolymer Stabilizing CdS Quantum Dots for Synergistically Boosting Photoreduction of CO₂

Abstract

Artificial photosynthesis is a viable approach for transforming carbon dioxide (CO 2 ) into value-added chemicals driven by renewable solar energy. Studies on photocatalytic CO 2 reduction (CO 2 R) have thus been expedited in recent years. Cadmium sulfide quantum dots (CdS QDs) have been regarded as one of the most promising photocatalysts, offering a myriad of advantages for CO 2 R, such as a narrow band gap, quantum confinement effect, and tunable redox potential. However, CdS QDs usually suffer from photo, thermal, and oxidative instability. In this work, we demonstrate an effective method to endow CdS QDs by assembling them with amphiphilic metallopolymers to enhance their stability and synergistically increase their catalytic activity. The metallopolymers were synthesized via precise radical polymerization between 1-ethyl-3-vinylimidazolium bromide and rhenium(I)-N-(3-((4′-methoxy-[2,2′-bipyridin]-4-yl)oxy)propyl)acrylamide compounds. The resultant positively charged rhenium complex-containing metallopolymer (P(Re-IL)) underwent spontaneous assembly with the negatively charged thioglycolate-capped CdS QDs via electrostatic interaction, forming highly active and stable CdS/P(Re-IL) hybrids. The ultimate interfacial interaction between the two components in CdS/P(Re-IL) facilitated photoinduced electron transfer (PET) from CdS to the vicinal bipyridyl Re I (CO) 3 Cl derivatives, promoting the photocatalytic CO 2 reduction to CO with a high production rate and selectivity in a 25 mL-DMF/water (4:1 v/v) solution under LED 370 nm irradiation. For example, CdS/P(5% Re-IL) was the optimum catalyst in our system, showing the highest CO production rate of 38.3 mmol g −1 h −1 and selectivity of 93.8% within 2 h with no induction period, which is ranked among the top state-of-the-art CO 2 R photocatalysts in mixed organic-water media.

Advancements in semiconductor quantum dots: expanding frontiers in optoelectronics, analytical sensing, biomedicine, and catalysis

“…Effective electron transfer and improved stability of CdS CQDs were identified as the reasons for the synergistic impact between the P(Re-IL) complex and CdS CQDs. 337 Another experiment involved the photocatalytic conversion of lignin oils and CO 2 into diesel precursors and H 2 /syngas using a heterogeneous photocatalytic system free of noble metals and made of electrostatically self-assembled CdSe CQDs/B-SiO 2 . The spherical SiO 2 carrier efficiently circulated the CdSe CQDs, improving the availability of active sites.…”

Regulating the Flexibility to Assemble Porous Single-Atom Fe-Coordinated Metallopolymers for Efficient Heterogeneous Catalytic Oxidations

“…For example, the 1D metallopolymer with Co–O 4 sites has been synthesized and self-assembled to show excellent performance for oxygen evolution reaction . Moreover, the amphiphilic metallopolymers hybridized with the CdS quantum dots by self-assembly endow them with synergistically boosting photoreduction of CO 2 . On the other hand, the utilization of dynamic covalent bonding, such as imine bonds, not only enhances crystallinity but also enables the design of dentate, tridentate, and tetradentate coordination structures to form single-atom metallopolymers. , The classic pincer structure, a frequently employed tridentate coordination mode, exhibits strong chelating ability while maintaining a semiopen structure that promotes interactions between the active sites and reactants.…”

General Pyrolysis for High-Loading Transition Metal Single Atoms on 2D-Nitro-Oxygeneous Carbon as Efficient ORR Electrocatalysts

“…On the other hand, their nonuniform active sites and low atomic utilization efficiency usually lead to lower chemical selectivity and reactivity compared to HOMs, as only limited numbers of active sites on the catalysts’ surface accessible to the reactants can play roles in reactions. There has been an idea to incorporate the merits of HOMs and HETs altogether by fixing the homogeneous catalysts such as organometallic complexes on solid substrates, − but this concept has not been widely applicable in industry yet, in spite of making great research efforts. This could possibly be because of the low endurance and complexity of the synthesis.…”