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This paper reports a robust strategy to catalyze in situ C–H oxidation by combining cobalt (Co) single-atom catalysts (SACs) and horseradish peroxidase (HRP). Co SACs were synthesized using the complex of Co phthalocyanine with 3-propanol pyridine at the two axial positions as the Co source to tune the coordination environment of Co by the stepwise removal of axial pyridine moieties under thermal annealing. These structural features of Co sites, as confirmed by infrared and X-ray absorption spectroscopy, were strongly correlated to their reactivity. All Co catalysts synthesized below 300 °C were inactive due to the full coordination of Co sites in octahedral geometry. Increasing the calcination temperature led to an improvement in catalytic activity for reducing O2, although molecular Co species with square planar coordination obtained below 600 °C were less selective to reduce O2 to H2O2 through the two-electron pathway. Co SACs obtained at 800 °C showed superior activity in producing H2O2 with a selectivity of 82–85% in a broad potential range. In situ production of H2O2 was further coupled with HRP to drive the selective C–H bond oxidation in 2-naphthol. Our strategy provides new insights into the design of highly effective, stable SACs for selective C–H bond activation when coupled with natural enzymes. 

Ion selective electrode (ISE) sensors have been broadly applied for real-time in situ monitoring of ion concentrations in water environments. However, ISE sensors suffer from critical problems, such as ionophore leaching, water-penetration, poor electrochemical stability, and resulting short life spans. In this study, a template-guided membrane matrix immobilization strategy was pursued as a novel ISE sensor fabrication methodology to enhance its sensing characteristics and longevity. Specifically, nano-porous anodized aluminum oxide (AAO) was used as the template for an NH 4 + -specific ISE sensor. A nano-porous nickel mesh eventually replaced the template and formed a compact, high-surface juncture with the NH 4 + ion-selective membrane matrix. The resulting template-guided nano-mesh ISE (TN-ISE) sensor displayed enhanced electrochemical stability ( i.e. , capacitance increased by 50%, reading drift reduced by 75%) when compared to a regular single-wall carbon nanotube (SW-CNT) ISE sensor used as the standard. The interface between the nano-mesh electrode and the ion selective membrane matrix was compact enough to prevent water influx at the electrode interface. This minimized ionophore leaching and increased the mechanical integrity of the TN-ISE sensor. The practical advantages of the novel sensor were validated via long-term (360 hours) tests in real wastewater, returning a small average error of 1.28% over this time. The results demonstrate the feasibility of the template-guided nano-mesh design and fabrication strategy toward ISEs for long-term continuous monitoring of water or wastewater quality. 

Abstract Converting CO₂to value‐added chemicals,e. g., CH₃OH, is highly desirable in terms of the carbon cycling while reducing CO₂emission from fossil fuel combustion. Cu‐based nanocatalysts are among the most efficient for selective CO₂‐to‐CH₃OH transformation; this conversion, however, suffers from low reactivity especially in the thermodynamically favored low temperature range. We herein report ultrasmall copper (Cu) nanocatalysts supported on crystalline, mesoporous zinc oxide nanoplate (Cu@mZnO) with notable activity and selectivity of CO₂‐to‐CH₃OH in the low temperature range of 200–250 °C. Cu@mZnO nanoplates are prepared based on the crystal‐crystal transition of mixed Cu and Zn basic carbonates to mesoporous metal oxides and subsequent hydrogen reduction. Under the nanoconfinement of mesopores in crystalline ZnO frameworks, ultrasmall Cu nanoparticles with an average diameter of 2.5 nm are produced. Cu@mZnO catalysts have a peak CH₃OH formation rate of 1.13 mol h⁻¹per 1 kg under ambient pressure at 246 °C, about 25 °C lower as compared to that of the benchmark catalyst of Cu−Zn−Al oxides. Our new synthetic strategy sheds some valuable insights into the design of porous catalysts for the important conversion of CO₂‐to‐CH₃OH.