Carbon dioxide (CO₂) is an abundant, nontoxic C1 feedstock, and (hetero)aromatic carboxylic acids are crucial structural frameworks and synthetic precursors in organic, materials, and medicinal chemistry. In this study, we present the deposition of a polyoxometalate@copper (SiW₁₂@Cu NP) catalyst on copper foam via a simple electrodeposition method (potential range: 0.6 to −0.8 V; scan rate: 50 mV·s⁻¹) for the electrocatalytic carboxylation of halo-(hetero)aromatic hydrocarbons with CO₂. The composite electrode leverages the synergistic effects of SiW₁₂ (redox stability, Lewis acidity) and Cu nanoparticles (multivalent states, high conductivity), enhancing electron transfer and CO₂ activation. Under mild reaction conditions (room temperature, 1 atm CO₂, and the absence of noble metals), the prepared catalytic system enables direct carboxylation of not only arenes but also electron-deficient (hetero)arenes, such as halopyridines, with CO₂, achieving a target product yield of over 65% in merely 40 min at a current density of 20 mA. Mechanistic studies confirm that the reaction is initiated by substrate electroreduction, followed by CO₂ fixation. This strategy simplifies the modification of drug intermediates, avoids structural damage to sensitive molecules, and optimizes drug properties through post-carboxylation, providing sustainable technical support for innovation in medicinal chemistry.

The selective oxidation of inert C(sp³)–H bonds in alkylbenzene remains a critical challenge in synthetic chemistry, necessitating advanced catalytic systems for sustainable C–H functionalization. Herein, we present a quinolinium-functionalized Anderson-type polyoxometalate (POM) (TBA-6MQ-Al) that achieves a toluene conversion of 64.24% and a benzoic acid yield of 57.32% under mild visible light (40 W 420−430 nm blue light-emitting diode (LED)), outperforming conventional POM-based photocatalysts. Systematic investigations reveal that methyl substitution on the quinolinium ligand enhances intersystem crossing efficiency, promoting triplet state formation for efficient O₂ activation. Radical quenching and electronic paramagnetic resonance (EPR) spectroscopy confirm superoxide/hydroxyl radicals and photogenerated electrons as key reactive species, whereas density functional theory (DFT) calculations elucidate the electronic structure–activity relationship. This work establishes a molecular engineering paradigm for optimizing POM redox properties, advancing sustainable C–H oxidation strategies with potential applications in green catalysis.

Several polyoxometalates (POMs) have been shown to possess antitumor activity. In this study, hydrophilic POMs were combined with the hydrophobic drug podophyllotoxin (PPT) to create an amphiphilic anti-cancer drug PPT-POM-PPT, which can self-assemble into hollow vesicles. The properties of these vesicles, such as the critical aggregation concentration, were characterized. These vesicles had low hemolytic activity and high stability. Cytotoxicity tests showed that the PTT-POM-PPT vesicles exhibit strong antitumor activity against lung and liver cancer cells without significantly affecting normal cells. Cell uptake experiments confirm that the PPT-POM-PPT vesicles can easily penetrate cell membranes and effectively enter tumor cells, thus exerting anti-tumor effects. Furthermore, these vesicles co-localized with lysosomes. Moreover, these PPT-POM-PPT vesicles exhibit synergistic effects of PPT and POMs. They are efficient drug delivery platforms that act as both the carrier and the active drug, avoiding the potential risks associated with additional carrier ingredients. In summary, due to their anticancer properties, POMs and PPT facilitate the generation of novel amphiphilic self-assembling vesicles, providing a theoretical basis and enabling clinical applications of POMs in cancer therapy.

Electro/photocatalytic carbon dioxide (CO₂) reduction to value-added chemicals and fuels is being actively studied as a promising pathway for renewable energy storage and climate change mitigation. Because of inert molecular properties and competing hydrogen generation reactions, high-performance electrocatalysts with high Faradaic efficiency and product selectivity but low overpotential are urgently needed. Polyoxometalates (POMs) are a class of polynuclear metal oxide clusters with a precise atomic structure, providing an ideal research platform to reveal the relationship between macroscopic properties and microstructures. Moreover, their highly tunable redox properties and abundant transition metal atom composition ensure thriving research for POM-based nanostructures toward CO₂ reduction. In this review, we first introduce the specific roles of POMs in electro/photocatalytic CO₂ reduction. Recent advances in POM-based nanostructures ranging from single clusters, assemblies, organic–inorganic hybrids to derivatives are systematically summarized. In particular, the structure–performance relationship of POM-based nanostructures is discussed at the atomic and molecular levels. Finally, the challenges and opportunities in the design of high-efficiency POM-based nanostructures are discussed to promote electro/photocatalytic CO₂ reduction.

Electroreduction of greenhouse gas CO₂ into value-added fuels and chemicals provides a promising pathway to address the issues of energy crisis and environmental change. However, the regulations of the selectivity towards C₂ product and the competing hydrogen evolution reaction (HER) are major challenges for CO₂ reduction reaction (CO₂RR). Here, we develop an interface-enhanced strategy by depositing a thin layer of nitrogen-doped graphene (N-G) on a Cu foam surface (Cu-N-G) to selectively promote the ethanol pathway in CO₂RR. Compared to the undetectable ethanol selectivity of pure Cu and Cu@graphene (Cu-G), Cu-N-G has boosted the ethanol selectivity to 33.1% in total Faradic efficiency (FE) at −0.8 V vs. reversible hydrogen electrode (RHE). The experimental and density functional theory (DFT) results verify that the interconnected graphene coating can not only serve as the fast charge transport channel but also provide confined nanospace for mass transfer. The N doping can not only trigger the intrinsic interaction between N in N-G and CO₂ molecule for enriching the local concentration of reactants but also promote the average valence state of Cu for C–C coupling pathways. The confinement effect at the interface of Cu-N-G can not only provide high adsorbed hydrogen (H_ad) coverage but also stabilize the key *HCCHOH intermediate towards ethanol pathway. The provided interface-enhanced strategy herein is expected to inspire the design of Cu-based CO₂RR electrocatalysts towards multi-carbon products.