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Photo-assisted technologies for environmental remediation
Industrial processes can lead to air and water pollution, particularly from organic contaminants such as toluene and antibiotics, posing threats to human health. Photo-assisted chemical oxidation technologies leverage light energy to mineralize these contaminants. In this Review, we discuss the mechanisms and efficiencies of photo-assisted advanced oxidation processes for wastewater treatment and photothermal technologies for air purification. The integration of solar energy enhances degradation efficiency and reduces energy consumption, enabling more efficient remediation methods. We evaluate the technological aspects of photo-assisted technologies, such as photo-Fenton, photo-persulfate activation, photo-ozonation and photoelectrochemical oxidation, emphasizing their potential for practical applications. Finally, we discuss the challenges in scaling up photo-assisted technologies for specific environmental remediation needs. Photo-assisted technologies have demonstrated effectiveness in environmental remediation, although large-scale applications remain constrained by high costs. Future potential applications of photo-assisted technologies will require that technology selection be tailored to specific pollution scenarios and engineering processes optimized to minimize costs.
Modeling the impact of structure and coverage on the reactivity of realistic heterogeneous catalysts
Adsorbates often cover the surfaces of catalysts densely as they carry out reactions, dynamically altering their structure and reactivity. Understanding adsorbate-induced phenomena and harnessing them in our broader quest for improved catalysts is a substantial challenge that is only beginning to be addressed. Here we chart a path toward a deeper understanding of such phenomena by focusing on emerging in silico modeling methodologies, which will increasingly incorporate machine learning techniques. We first examine how adsorption on catalyst surfaces can lead to local and even global structural changes spanning entire nanoparticles, and how this affects their reactivity. We then evaluate current efforts and the remaining challenges in developing robust and predictive simulations for modeling such behavior. Last, we provide our perspectives in four critical areas—integration of artificial intelligence, building robust catalysis informatics infrastructure, synergism with experimental characterization, and adaptive modeling frameworks—that we believe can help surmount the remaining challenges in rationally designing catalysts in light of these complex phenomena.
Anion vacancies activate N2 to ammonia on Ba–Si orthosilicate oxynitride-hydride
Anion vacancies on metal oxide surfaces have been studied as either active sites or promoting sites in various chemical reactions involving oxidation/reduction processes. However, oxide materials rarely work effectively as catalysts in the absence of transition metal sites. Here we report a Ba–Si orthosilicate oxynitride–hydride as a transition-metal-free catalyst for efficient ammonia synthesis via an anion-vacancy–mediated mechanism. The facile desorption of H− and N3− anions plus the flexibility of the crystal structure can accommodate a high density of electrons at vacancy sites, where N2 can be captured and directly activated to ammonia through hydrogenation processes. The ammonia synthesis rates reach 40.1 mmol g−1 h−1 at 300 °C by loading ruthenium nanoparticles. Although not found to dissociate N2, Ru instead facilitates the formation of anion vacancies at the Ru–support interface. This demonstrates a new route for anion-vacancy–mediated heterogeneous catalysis.
Urine electrooxidation for energy–saving hydrogen generation
Urea electrooxidation offers a cost-effective alternative to water oxidation for energy-saving hydrogen production. However, its practical application is limited by expensive urea reactants and sluggish reaction kinetics. Here, we present an efficient urine electrolysis system for hydrogen production, using cost-free urine as feedstock. Our system leverages a discovered Cl-mediated urea oxidation mechanism on Pt catalysts, where adsorbed Cl directly couple with urea to form N-chlorourea intermediates, which are then converted into N2 via intermolecular N–N coupling. This rapid mediated-oxidation process notably improves the activity and stability of urine electrolysis while avoiding Cl-induced corrosion, enabling over 200 hours of operation at reduced voltages. Accordingly, a notable reduction in the electricity consumption is achieved during urine electrolysis (4.05 kWh Nm−3) at 300 mA cm−2 in practical electrolyser for hydrogen production, outperforming the traditional urea (5.62 kWh Nm−3) and water (4.70–5.00 kWh Nm−3) electrolysis.
Strong-weak dual interface engineered electrocatalyst for large current density hydrogen evolution reaction
Supported nanocatalysts are crucial for hydrogen production, yet their activity and stability are challenging to manage due to complex metal-support interfaces. Herein, we design Pt@ anatase&rutile-TiO2 with a strong-weak dual interface by modifying TiO2 using high-energy ball milling and in-situ reduction to vary surface energies. Experiments and density functional theory calculations reveal that the strong Pt-anatase TiO2 interface enhances hydrogen adsorption. In contrast, the weak Pt-rutile TiO2 interface facilitates hydrogen desorption, simultaneously preventing Pt agglomeration and increasing reaction rate. As a result, the tailored catalyst has a 529.3 mV overpotential at 1000 mA cm−2 in 0.5 M H2SO4, 0.69 times less than commercial Pt/C. It also possesses 8.8 times the mass activity of commercial Pt/C and maintains a low overpotential after 2000 cyclic voltammetry cycles, suggesting high activity and stability. This strong-weak dual interface engineering strategy shows potential for overall water splitting and proton exchange membrane water electrolyzer, advancing the design of efficient supported nanocatalysts.
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