Search

Exfoliation into a 2D nanosheet structure can lead to enhanced surface activity and unique optical and electronic properties in polymeric carbon nitride (PCN). In this study, four common exfoliation strategies (liquid ultrasonication, thermal oxidation, hydrothermal oxidation, and chemical oxidation) were adopted, and their effects on the structural and electronic changes in PCN were analyzed in detail. This allows us to understand the relationship between the exfoliation mechanism and the structural/optical properties. Here, we demonstrate that the thermal and ultrasonic exfoliation methods can effectively reduce the thickness of PCN while preserving its original structure. In contrast, the chemical and hydrothermal treatments can strongly affect the morphology and structure of PCN, leading to a decreased performance in phenol photodegradation. Therefore, depending on the employed exfoliation method, the surface area, functionalization, band edge positions, charge carrier generation, and mobility are influenced differently up to the point where semiconducting behavior is entirely lost. Our results allow conclusions about the applicability of the different exfoliation methods to obtain distinct material properties for photocatalytic applications. [ABSTRACT FROM AUTHOR]

Reverse water-gas shift (RWGS) reaction has attracted much attention as a potential approach for CO 2 valorization via the production of synthesis gas, especially over Fe-modified supported Cu catalysts on CeO 2 . However, most studies have focused solely on investigating the RWGS reaction over catalysts with high Cu and Fe loadings, thus leading to an increase in the complexity of the catalytic system and, hence, preventing the gain of any reliable information about the nature of the active sites and reaction mechanism. In this work, a CeO 2 -supported single-atom Cu catalyst modified with iron was synthesized and evaluated for the RWGS reaction. The catalytic results reveal a significant synergistic effect between CuCeO 2 and Fe, demonstrating an activity up to three times higher than the combined catalytic activities of monometallic catalysts (Fe/CeO 2 + CuCeO 2 ) under identical conditions. Various ex situ and in situ/operando techniques are employed to unveil the concealed role of Fe in catalyst activity enhancement. The combined findings from hydrogen temperature-programmed reduction (H 2 -TPR) and operando electron paramagnetic resonance spectroscopy (EPR) reveal that the added Fe predominantly interacts with Cu-containing surface sites, resulting in the stabilization of higher proportions of Cu single sites. Near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) and operando EPR results unveil a synergistic interplay of Fe with Cu-containing sites and CeO x domains, efficiently enhancing both the reoxidation of Cu + in Cu + -O v -Ce 3+ moieties and the reducibility of Ce 4+ in CeO x domains under RWGS conditions. Detailed mechanistic studies reveal that the RWGS reaction predominantly proceeds via the redox mechanism., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Co-axial electrospinning was applied for the structuring of non-woven webs of TiO 2 nanofibers loaded with Ag, Au, and CuO nanoparticles. The composite layers were tested in an electrochromic half-cell assembly. A clear correlation between the nanoparticle composition and electrochromic effect in the nanofibrous composite is observed: TiO 2 loaded with Ag reveals a black-brown color, Au shows a dark-blue color, and CuO shows a dark-green color. For electrochromic applications, the Au/TiO 2 layer is the most promising choice, with a color modulation time of 6 s, transmittance modulation of 40%, coloration efficiency of 20 cm 2 /C, areal capacitance of 300 F/cm 2 , and cyclic stability of over 1000 cycles in an 18 h period. In this study, an unexplored path for the rational design of TiO 2 -based electrochromic device is offered with unique color-switching and optical efficiency gained by the fibrous layer. It is also foreseen that co-axial electrospinning can be an alternative nanofabrication technique for smart colored windows., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Investigating a catalyst under relevant application conditions is experimentally challenging and parameters like reaction conditions in terms of temperature, pressure, and reactant mixing ratios, as well as catalyst design, may significantly impact the obtained experimental results. For Pt catalysts widely used for the oxidation of carbon monoxide, there is keen debate on the oxidation state of the surface at high temperatures and at/above atmospheric pressure, as well as on the most active surface state under these conditions. Here, we employ a nanoreactor in combination with single-particle plasmonic nanospectroscopy to investigate individual Pt catalyst nanoparticles localized inside a nanofluidic model pore during carbon monoxide oxidation at 2 bar in the 450-550 K temperature range. As a main finding, we demonstrate that our single-particle measurements effectively resolve a kinetic phase transition during the reaction and that each individual particle has a unique response. Based on spatially resolved measurements, we furthermore observe how reactant concentration gradients formed due to conversion inside the model pore give rise to position-dependent kinetic phase transitions of the individual particles. Finally, employing extensive electrodynamics simulations, we unravel the surface chemistry of the individual Pt nanoparticles as a function of reactant composition and find strongly temperature-dependent Pt-oxide formation and oxygen spillover to the SiO 2 support as the main processes. These results therefore support the existence of a Pt surface oxide in the regime of high catalyst activity and demonstrate the possibility to use plasmonic nanospectroscopy in combination with nanofluidics as a tool for in situ studies of individual catalyst particles., Competing Interests: The authors declare no competing financial interest., (© 2021 American Chemical Society.)

It is generally accepted that optimal particle sizes are key for efficient nanocatalysis. Much less attention is paid to the role of morphology and atomic arrangement during catalytic reactions. Here, we unravel the structural, stoichiometric, and morphological evolution of gas-phase produced and partially oxidized cobalt nanoparticles in a broad size range. Particles with diameters between 1.4 and 22 nm generated in cluster sources are size selected and deposited on amorphous alumina (Al2O3) and ultrananocrystalline diamond (UNCD) films. A combination of different techniques is employed to monitor particle properties at the stages of production, exposure to ambient conditions, and catalytic reaction, in this case, the oxidative dehydrogenation of cyclohexane at elevated temperatures. A pronounced size dependence is found, naturally classifying the particles into three size regimes. While small and intermediate clusters essentially retain their compact morphology, large particles transform into hollow spheres due to the nanoscale Kirkendall effect. Depending on the substrate, an isotropic (Al2O3) or anisotropic (UNCD) Kirkendall effect is observed. The latter results in dramatic lateral size changes. Our results shed light on the interplay between chemical reactions and the catalyst's structure and provide an approach to tailor the cobalt oxide phase composition required for specific catalytic schemes.