Carbonylation reactions are fundamental for constructing carbonyl-containing molecules, yet their industrial implementation remains constrained by harsh operating conditions and the frequent reliance on precious metal catalysts. Photocatalysis provides a compelling alternative, enabling carbonylation under much milder conditions. In this Perspective, we examine recent advances in this research field, placing particular emphasis on heterogeneous catalytic systems. We first introduce key homogeneous examples and the representative reaction pathways, including the radical-mediated process and the photo-induced generation of unsaturated metal carbonyl complexes, along with various substrate types and the challenges associated with homogeneous systems. We then discuss the emerging examples in heterogeneous systems. Drawing on knowledge established in homogeneous catalysis and combining the advantages of heterogeneous catalysis, we identify promising research directions in porous framework materials, semiconductor photocatalysts, and reactor design for developing efficient heterogeneous carbonylation systems. Looking forward, we anticipate that heterogenized photocatalytic carbonylation represents a promising route toward more sustainable and industrially viable carbonylative processes.

As a common mineral phase on Earth and Martian regolith, natural rutile was reported as a potential candidate for use as a Fenton catalyst in this study. The influences of Fe and V in various chemical states on the generation of reactive oxygen species (ROSs) and the catalytic activity of rutile were examined. A series of rutile samples with various surface and bulk states of Fe and V were obtained initially by hydrogen annealing of natural rutile at ~773–1173 K. X-ray diffraction, electron paramagnetic resonance spectra, and X-ray photoelectron spectroscopy demonstrated that the atomic fractions of Fe(III) and V(V) decreased sharply with increasing temperature, along with the accumulation of surface Fe(II) and bulk V(III). All as-prepared materials showed enhanced Fenton degradation efficiency on methylene blue (MB) compared with P25-TiO2, and the treated samples exhibited up to 3.5-fold improvement in efficiency at pH 3 compared to the untreated sample. The improved efficiency was attributed mainly to Fenton catalysis involving Fe(II) and V(III). The dissolved Fe2+ played a crucial role in the homogeneous Fenton reaction, while the bound V(III) favored adsorption primarily and may have facilitated heterogeneous Fenton reaction and the regeneration of Fe2+. The pH regulated the reaction mechanism among homogeneous (pH = 3) and heterogeneous (pH = 3.7) Fenton catalysis and physical adsorption (pH = 5, 6). The aim of the present study was to improve the understanding of the potential role of natural rutile with advanced oxidation functions in Earth systems and even on Mars, which also provide an inspiration for screening natural rutile and any other similar, Earth-abundant, low-cost minerals for environmental application.

The synthesis of copper citrate complex supported on acid-activated vermiculite was investigated with a view to preparing an efficient, mild, robust and recyclable catalyst for the Biginelli reaction. The new catalyst was characterized by X-ray fluorescence (XRF), infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray powder diffraction (XRD), and scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDS). Copper citrate supported over activated vermiculite (AAVrm-Cu2) showed good catalytic activity in the synthesis of 3,4-dihydropyrimidinones. The catalyst can be separated easily from the reaction mixture by filtration and retains its catalytic activity for up to five cycles of reaction with no apparent decrease in yield.

A simple and efficient method for in situ preparation of highly stable polyimide (PI)-supported silver nanoparticles (AgNPs) was proposed. This process achieves excellent dispersion and high stability of AgNPs in the PI matrix. The formation of AgNPs in PI and the morphology evolution of PI/Ag nanocomposites were characterized by x-ray diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy (FT-IR), and x-ray photoelectron spectra studies. The catalytic properties of these PI-supported AgNPs were investigated by monitoring the reduction of 4-nitrophenol by excess NaBH4 in water. The catalytic reaction was observed to have a pseudo first-order rate constant of 0.567 min−1 (9.45 × 10−3 s−1), which is comparable to other heterogeneous silver catalysts reported in the literature. Notably, the PI-supported AgNPs retained their relatively high catalytic activity over seven recycles with almost no leaching of catalytic species in the reaction solution. Moreover, the catalytic activity of the catalyst is still quite appreciable even after a six-month shelf-storage under room temperature.