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The electrochemical reduction of CO2 to produce high-value multicarbon products represents a challenging yet highly desirable process, particularly due to the inefficient C–C coupling observed in current electrocatalysts. In this study, Cu2+ and Co2+ were introduced into ZIF-8 as precursors to synthesize a series of Co- and CuCo-doped carbon nanostructure materials with varying Co-to-Cu ratios. X-ray diffraction and X-ray photoelectron spectroscopy (XPS) analyses confirmed the successful doping of metal Co in the form of Co–Nx, while Cu was partly doped as nanoparticles attached to the carbon substrate surface and partly as single atoms forming Cu–Nx. Transmission electron microscopy and energy-dispersive X-ray spectroscopy analyses revealed uniform distribution of elemental Co and Cu on the carbon substrate, with Cu loaded as nanocluster on the surface. Linear sweep voltammetry tests indicated that Cu/CoCu-Nx-C composites exhibited enhanced reactivity toward CO2 reduction compared to other samples. At −0.19 V (vs RHE), the Faradaic efficiencies (FEs %) of C2H4, C2H6, CH4, CO, and H2 over Cu/CoCu-Nx-C were 29.7, 8.6, 20.2, 9.8, and 31.5%, respectively. The influence of Co and Cu doping modes on the selectivity of electrocatalytic reduction products was investigated. Results showed that Cu/CoCu-Nx-C exhibited a higher FE of C2 compared to Cu/Cu–Nx-C, with nearly 10 times higher C2 current density. Mechanistic insights from acid-etching experiments and XPS revealed a synergistic interaction between metallic Co and Cu, promoting the generation of multicarbon products. Co–Nx improved *CO coverage, facilitating subsequent C–C coupling on neighboring Cu–Nx. Additionally, CH4 production was attributed to the (111) crystalline facets in the Cu nanocluster and isolated Cu–Nx. Overall, this research provides an important understanding of the creation of straightforward and effective catalysts for the reduction of CO2. It holds considerable potential for the production of hydrocarbons using carbon dioxide. [ABSTRACT FROM AUTHOR]

The ring opening copolymerization (ROCOP) of epoxides and cyclic anhydrides is one of the most important ways to synthesize polyesters both in industrial and academic fields. Herein, the zeolitic imidazolate framework‐67 (ZIF‐67) was used as a heterogeneous catalyst for the ROCOP of epoxides and cyclic anhydrides without co‐catalyst and initiator. Notably, the obtained polyesters with alternate structures were proved by the 1H NMR spectrum and FTIR spectrum, which indicate the ROCOP is alternatively copolymerized. Kinetic study of the ROCOP of cyclohexene oxide (CHO) and phthalic anhydride (PA) shows that the polymerization reaction is first‐order kinetics. The apparent activation energy (Ea) of the ROCOP of CHO and PA catalyzed by ZIF‐67 was found to be about 104.4 KJ/mol. A possible mechanism of ROCOP of CHO and PA is that the metal Co coordinates with the oxygen atom on the monomer to weaken the C‐O bond thereby opening the ring structure and initiating the copolymerization reaction. In this study, a new system for the copolymerization of epoxide and anhydride catalyzed by heterogeneous catalysts was discovered, which has important guiding significance. [ABSTRACT FROM AUTHOR]

Photo‐induced reversible complexation‐mediated polymerization (RCMP) is a green and economical method to prepare polymers with precise molecular weights, narrow molecular weight distributions and functionally active chain ends. Covalent organic frameworks (COFs) are a promising heterogeneous photocatalyst for mediating RCMP due to their adjustable structure, band gap, and porosity. In this work, 1,3,5‐triformylphloroglucinol (Tp) and p‐azoaniline (Azo) were selected to construct 2D β‐ketoenamine linked Tp‐Azo‐COF as a heterogeneous photocatalyst to trigger RCMP under white light irradiation. A series of polymers with controllable molecular weight and narrow molecular weight distribution were successfully prepared by using Tp‐Azo‐COF as photocatalysis. On/off light experiments confirmed the good spatiotemporal control feature, and chain expansion experiments demonstrated the high "activity" of polymer chain ends. Furthermore, the mechanistic research elucidated that electron transfer between Tp‐Azo‐COF and initiator occurred, allowing the formation of reactive radicals to mediate RCMP. Density functional theory calculations revealed that the coordination of iodine on the initiator to catalyst obviously reduced the bond dissociation energy, leading to enhance in the polymerization rate. This work provides a platform for constructing heterogeneous photocatalysts with more efficient and stable to mediate RCMP. [ABSTRACT FROM AUTHOR]