ABSTRACT
Efficient conversion of biomass wastes into valuable chemicals has been regarded as a sustainable approach for green and circular economy. Herein, a highly efficient catalytic conversion of glycerol (Gly) into glycerol carbonate (GlyC) by carbonylation with the commercially available urea is presented using low-cost transition metal single atoms supported on zinc oxide quantum dots (M1-ZnO QDs) as a catalyst without using any solvent. A facile one-step wet chemical synthesis allows various types of metal single atoms to simultaneously dope and introduce Lewis-acid defects in the ZnO QD structure. It is found that doping with a trace amount of isolated metal atoms greatly boosts the catalytic activity with Gly conversion of 90.7%, GlyC selectivity of 100.0%, and GlyC yield of 90.6%. Congruential results from both Density Functional Theory (DFT) and in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (in situ DRIFTS) studies reveal that the superior catalytic performance can be attributed to the enriched Lewis acid sites that endow optimal adsorption, formation of the intermediate for coupling between urea and Gly, and desorption of GlyC. Moreover, the tiny size of ZnO QDs efficiently promotes the accessibility of these active sites to the reactants.
ABSTRACT
Metal single-site catalysts have recently played an essential role in catalysis due to their enhanced activity, selectivity, and precise reaction control compared to those of conventional metal cluster catalysts. However, the rational design and catalytic application of metal single-site catalysts are still in the early stages of development. In this contribution, we report the rational design of Fe single sites incorporated in a hierarchical ZSM-5 via atomic layer deposition (ALD). The designer catalysts demonstrated highly dispersed Fe species, predominantly stabilized by oxygen atoms in the zeolite framework at terminal, isolated, and vicinal silanol groups within the micropores and external surfaces of the zeolite. The successful incorporation of highly thermally stable and uniform Fe single sites into hierarchical zeolite through ALD represents a significant advancement in few-walled carbon nanotube production. The inner and outer diameters of produced CNTs are approximately 4.4 ± 2.4 and 8.6 ± 1.8 nm, respectively, notably smaller than those produced via traditional impregnated catalysts. This example emphasizes the concept of rational design of a single Fe site dispersed on a hierarchical ZSM-5 surface, which is anticipated to be a promising catalyst for advancing catalytic applications.
ABSTRACT
Single-atom catalysts (SACs) possess the potential to involve the merits of both homogeneous and heterogeneous catalysts altogether and thus have gained considerable attention. However, the large-scale synthesis of SACs with rich isolate-metal sites by simple and low-cost strategies has remained challenging. In this work, we report a facile one-step pyrolysis that automatically produces SACs with high metal loading (5.2-15.9 wt %) supported on two-dimensional nitro-oxygenated carbon (M1-2D-NOC) without using any solvents and sacrificial templates. The method is also generic to various transition metals and can be scaled up to several grams based on the capacity of the containers and furnaces. The high density of active sites with N/O coordination geometry endows them with impressive catalytic activities and stability, as demonstrated in the oxygen reduction reaction (ORR). For example, Fe1-2D-NOC exhibits an onset potential of 0.985 V vs RHE, a half-wave potential of 0.826 V, and a Tafel slope of -40.860 mV/dec. Combining the theoretical and experimental studies, the high ORR activity could be attributed its unique FeO-N3O structure, which facilitates effective charge transfer between the surface and the intermediates along the reaction, and uniform dispersion of this active site on thin 2D nanocarbon supports that maximize the exposure to the reactants.
ABSTRACT
The discoveries of 2D nanomaterials have made huge impacts on the scientific community. Their unique properties unlock new technologies and bring significant advances to diverse applications. Herein, an unprecedented 2D-stacked material consisting of copper (Cu) on nitro-oxygenated carbon is disclosed. Unlike any known 2D stacked structures that are usually constructed by stacking of separate 2D layers, this material forms a continuously folded 2D-stacked structure. Interestingly, advanced characterizations indicate that Cu atoms inside the structure are in an atomically-dispersed form with extraordinarily high Cu loading up to 15.9 ± 1.2 wt.%, which is among the highest reported metal loading for single-atom catalysts on 2D supports. Facile exfoliation results in thin 2D nanosheets that maximize the exposure of the unique active sites (two neighboring Cu single atoms), leading to impressive catalytic performance, as demonstrated in the electrochemical oxygen reduction reaction.
Subject(s)
Copper , Nanostructures , Humans , Carbon , Catalysis , HypoxiaABSTRACT
The development of fast and non-invasive techniques to detect SARS-CoV-2 virus at the early stage of the infection would be highly desirable to control the COVID-19 outbreak. Metal-organic frameworks (MOFs) are porous materials with uniform porous structures and tunable pore surfaces, which would be essential for the selective sensing of the specific COVID-19 biomarkers. However, the use of MOFs materials to detect COVID-19 biomarkers has not been demonstrated so far. In this work, for the first time, we employed the density functional theory calculations to investigate the specific interactions of MOFs and the targeted biomarkers, in which the interactions were confirmed by experiment. The five dominant COVID-19 biomarkers and common exhaled gases are comparatively studied by exposing them to MOFs, namely MIL-100(Al) and MIL-100(Fe). The adsorption mechanism, binding site, adsorption energy, recovery time, charge transfer, sensing response, and electronic structures are systematically investigated. We found that MIL-100(Fe) has a higher sensing performance than MIL-100(Al) in terms of sensitivity and selectivity. MIL-100(Fe) shows sensitive to COVID-19 biomarkers, namely 2-methylpent-2-enal and 2,4-octadiene with high sensing responses as 7.44 x 105 and 9 x 107 which are exceptionally higher than those of the common gases which are less than 6. The calculated recovery times of 0.19 and 1.84 x 10-4 s are short enough to be a resuable sensor. An experimental study also showed that the MIL-100(Fe) provides a sensitivity toward 2-methylpent-2-enal. In conclusion, we suggest that MIL-100(Fe) could be used as a potential sensor for the exhaled breath analysis. We hope that our research can aid in the development of a biosensor for quick and easy COVID-19 biomarker detection in order to control the current pandemic.
ABSTRACT
In this study, ab initio calculations were performed to show that the superconductivity in Li-intercalated bilayer MoS2 could be enhanced by applying either compressive or tensile strain. Moreover, the mechanism for superconductivity enhancement for the tensile strain case was found to be different than that of the compressive strain case. Enhanced electron phonon coupling (EPC) under tensile strain could be explained by an increase in the nesting function involved with the change in the Fermi surface topology in a wide range of Brillouin zones. The superconducting transition temperature T c of 0.46 K at zero strain increased up to 9.12 K under a 6.0% tensile strain. Meanwhile, the enhancement in compressive strain was attributed to the increase in intrinsic electron phonon matrix elements. Furthermore, the contribution from interband scattering was large, which suggested the importance of electron pockets on the Fermi surface. Finally, 80% of the total EPC (λ = 0.98) originated from these pockets and the estimated T c was 13.50 K.
