ABSTRACT
The superior photocatalytic activity of TiO2 nanocrystals with exposed high-energy (001) facets, achieved through the use of hydrofluoric acid as a shape-directing reagent, is widely reported. However, in this study, we report for the first time the detrimental effect of surface fluorination on the photoreactivity of high-energy faceted TiO2 nanocrystals towards NO oxidation (resulting in a NO removal rate of only 5.9%). This study aims to overcome this limitation by exploring surface defluorination as an effective strategy to enhance the photocatalytic oxidation of NO on TiO2 nanocrystals enclosed with (001) facets. We found that surface defluorination, achieved through either NaOH washing (resulting in an improved NO removal rate of 23.2%) or calcination (yielding an enhanced NO removal rate of 52%), leads to a large increase in the photocatalytic oxidation of NO on TiO2 nanocrystals with enclosed (001) facets. Defluorination processes stimulate charge separation, effectively retarding recombination and significantly promoting the production of reactive oxygen species, including superoxide radicals (·O2-), singlet oxygen (1O2), and hydroxyl radicals (·OH). Both in situ diffuse reflectance infrared Fourier-transform spectroscopy and density functional theory calculations confirm the higher adsorption of NO after defluorination, thus facilitating the oxidation of NO on TiO2 nanocrystals.
ABSTRACT
Electrocatalytic and thermocatalytic CO2 conversions provide promising routes to realize global carbon neutrality, and the development of corresponding advanced catalysts is important but challenging. Hollow-structured carbon (HSC) materials with striking features, including unique cavity structure, good permeability, large surface area, and readily functionalizable surface, are flexible platforms for designing high-performance catalysts. In this review, the topics range from the accurate design of HSC materials to specific electrocatalytic and thermocatalytic CO2 conversion applications, aiming to address the drawbacks of conventional catalysts, such as sluggish reaction kinetics, inadequate selectivity, and poor stability. Firstly, the synthetic methods of HSC, including the hard template route, soft template approach, and self-template strategy are summarized, with an evaluation of their characteristics and applicability. Subsequently, the functionalization strategies (nonmetal doping, metal single-atom anchoring, and metal nanoparticle modification) for HSC are comprehensively discussed. Lastly, the recent achievements of intriguing HSC-based materials in electrocatalytic and thermocatalytic CO2 conversion applications are presented, with a particular focus on revealing the relationship between catalyst structure and activity. We anticipate that the review can provide some ideas for designing highly active and durable catalytic systems for CO2 valorization and beyond.
ABSTRACT
Photo-oxidation with semiconductor photocatalysts provides a sustainable and green solution for NOx elimination. Nevertheless, the utilization of traditional photocatalysts in efficient and safe photocatalytic NOx removal is still a challenge due to the slow charge kinetic process and insufficient optical absorption. In this paper, we report a novel porous g-C3N4 nanosheet photocatalyst modified with cyano defects and CaCO3 (xCa-CN). The best performing sample (0.5Ca-CN) exhibits an enhanced photo-oxidation NO removal rate (51.18 %) under visible light irradiation, largely surpassing the value of pristine g-C3N4 nanosheets (34.05 %). Such an enhancement is mainly derived from an extended visible-light response, improved electron excitation and transfer, which are associated with the synergy of cyano defects and CaCO3, as evidenced by a series of spectroscopic analyses. More importantly, in-situ DRIFTS and density functional theory (DFT) results suggest that the introduction of cyano defects and CaCO3 enables control over NO adsorption and activation processes, making it possible to implement a preference pathway (NO â NO+ â NO3¯) and reduce the emission of toxic intermediate NO2. This work demonstrates the potential of integrating defect engineering and insulator modification to design highly efficient g-C3N4-based photocatalysts for air purification.
ABSTRACT
Optical coherence tomography (OCT) is becoming a clinically useful and important imaging technique due to its ability to provide high-resolution structural imaging in vivo. Optical coherence tomography angiography (OCTA) can visualize vasculature imaging of biological tissues. With the advent of Fourier-domain OCT, numerous OCTA techniques have been developed to detect the microvasculature in vivo. The macular region of the fundus is separated into retinal and choroid regions by segmentation algorithm in the data processing, a false blood flow signal is generated due to bulk motion when vasculature imaging was segmented in the retinal regions. However, the most recent OCT angiographic approaches are sensitive to bulk motion noise. To overcome this limitation, we proposed an improved speckle contrast optical coherence tomography angiography (ISC-OCTA) algorithm to image vasculature network in vivo. The improved speckle contrast image was acquired by the improved speckle contrast algorithm for N consecutive frames of the same location, and the vasculature of the tissue was generated by masking the averaged image with the improved speckle contrast image. ISC-OCTA was tested on in vivo images of a phantom mouse ear and a human macula. Compared to the recently reported algorithms, we found that ISC-OCTA can distinguish the dynamic information of blood flow from static tissue and visualize capillary vessels. Especially when the segmentation data generates false information, the ISC-OCTA algorithm has a significant effect on the suppression of the line noise. ISC-OCTA can provide clear visualization of vessels as other algorithms and may be useful in the diagnosis of ophthalmic diseases.