Thermocatalytic technologies are the most promising approach for converting plastic waste into valuable chemicals. The Ru-based catalysts are the most active catalysts reported, which are highly efficient for C–C bond breaking during thermocatalytic plastic degradation. Still, significant challenges remain in controlling the selectivity of the valuable liquid product. A trade-off relationship between the activity and selectivity is commonly found during thermocatalytic plastic degradation. Herein, we demonstrated that a Ru/γ-Al₂O₃-Ar catalyst, prepared from commercial γ-Al₂O₃ pre-calcined under an Ar atmosphere, achieved 100% conversion over low-density polyethylene (LDPE) hydrogenolysis and an 85.9% selectivity for fuel-range and wax hydrocarbons at 250 °C for 4 h. In contrast, Ru loaded on the synthesized γ-Al₂O₃ showed only a 17.9% selectivity toward fuel range and wax hydrocarbons, with methane being the predominant product. Comprehensive characterizations revealed a strong metal-support interaction (MSI) at the interface between Ru and γ-Al₂O₃-Ar, leading to the abundance of Ruⁿ⁺ species at the Ru-Al₂O₃ interface. Combined experimental and density functional theory (DFT) computational studies reveal that the incorporation of Ruⁿ⁺ effectively suppresses excessive dehydrogenation into methane intermediates. Simultaneously, it promotes the hydrogenation of hydrocarbon intermediates through a synergistic hydrogen spillover effect, driven by high H* coverage, which ultimately boosts catalytic efficiency.

Electrocatalytic oxidation of biomass-derived 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid offers a sustainable route to high-value chemicals. Anion doping in cobalt-based catalysts can modulate catalytic performance by altering the coordination environment and electronic structure of active sites, thereby affecting surface reconstruction and reaction kinetics. Here, anion-modified cobalt hydroxysalts (Co(OH)_2−x(A^m−)_x/m, A = CO₃, F, and Cl) were synthesized to investigate anion-specific effects on electrooxidation of 5-hydroxymethylfurfural. The carbonate-incorporated nanowire catalyst exhibited outstanding performance, lowering the oxidation potential to 1.33 V at 50 mA·cm⁻² and increasing the active site density by 1.5 times relative to undoped Co(OH)₂. In contrast, F⁻ and Cl⁻ doping led to redox potential shifts and reduced activity. In situ Raman spectroscopy revealed that the catalytic reaction was driven by active CoOOH species generated under anodic polarization. This process was accompanied by carbonate leaching and irreversible phase changes, which contributed to catalyst deactivation. This study provides insights into anion-controlled catalyst design for efficient and durable biomass electrooxidation.

Highly dispersed Pt-based single-atom alloys have been extensively studied in heterogeneous catalysis, particularly for propane dehydrogenation (PDH). However, Pt-based single-atom alloys still suffer from sintering and coke deposition in high-temperature dehydrogenation reactions. Additionally, the atomic structure of the active sites of Pt-based single-atom alloys for PDH remains elusive, and the solid chemistry occurring on the catalyst surface is still under debate. In this work, we discovered that the coordination environment of the single Pt atom for Pt₁Cu₃₀ cluster catalysts, encapsulated with a carbon layer, can be regulated by sequential heat treatment under air and H₂ atmosphere. The Pt₁Cu₃₀ cluster catalyst, with a single Pt atom coordinated by 9 Cu atoms, is similar to the surface structure of Pt₁Cu₃ (111) and exhibits excellent catalytic activity and stability at high temperatures, maintaining propane conversion of 43.5% and propylene selectivity of 98.2%, with a deactivation constant (K_d) of 0.01 h⁻¹, even after 32 h of testing at 600 °C. The combination of structural characterizations and temperature programmed analysis reveal that the single Pt atom coordinated by around 9 Cu atoms of the Pt₁Cu₃₀ cluster catalyst, serves as the vital active sites for C–H cleavage of propane and propylene desorption due to their electron-rich and geometrically isolated Pt atom structure. Furthermore, the thin carbon layer coated on the surface of Pt₁Cu₃₀ clusters can effectively reduce the desorption energy of propylene, thereby avoiding further dehydrogenation and improving the propylene yield and catalytic stability.