The control of morphology, structure and composition of metal-organic frameworks derived metal-nitrogen doped porous carbon (M-N-C) with high precision and accuracy is essential for the catalytic performance. While single-atom or small-sized nanometer catalysts show notable effects in catalysis, one catalyst combining the advantages of single-atom and nanometer catalysts may cultivate more benefits. Herein, we designed and successfully fabricated a series of Fe-doped ZIF-x with different morphologies (cube→truncated hexahedron→truncated octahedron) in one pot by simply adjusting the adding amount of vitamin C. After high-temperature calcination, FeC integrated with Fe single-atom planted in N-doped carbon (Fe/Fe-N-C-x) with various morphology, structure and composition could be acquired. Among them, Fe/Fe-N-C-0.75 exhibited the best catalytic performance for the transfer hydrogenation of halogenated nitrobenzenes with NH·HO under room temperature. Acid-leaching tests, poisoning experiments, and the density functional theory calculations showed that FeC integrated with Fe single-atom had a better catalytic effect than the separated FeC or Fe single-atom.
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http://dx.doi.org/10.1016/j.jcis.2023.03.006 | DOI Listing |
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December 2024
Yangtze Delta Region Institute (Huzhou), University of Electronic Science and Technology of China, Huzhou, 313001, P. R. China.
In recent years, single-atom catalysts (SACs) with separated active centers and high atom utilization have grown significantly as a significant area of catalytic research. In catalytic applications, SACs of various kinds have demonstrated exceptional performance, so the study of the catalytic mechanism of SACs provides a clearer direction for the preparation of catalysts with high performance. Strong linkages between the single atoms and the support are necessary to overcome the tendency of single atoms to aggregate into clusters, which is called metal-support interaction (MSI).
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December 2024
School of Materials Science and Engineering, Tianjin Key Laboratory of Composite and Functional Materials, Key Laboratory of Advanced Ceramics and Machining Technology of Ministry of Education, Tianjin University, Tianjin, 300350, P. R. China.
Atomically dispersed transition metal (ADTM) catalysts are widely implemented in energy conversion reactions, while the similar properties of TMs make it difficult to continuously improve the activity of ADTMs via tuning the composition of metals. Introducing nonmetal sites into ADTMs may help to effectively modulate the electronic structure of metals and significantly improve the activity. However, it is difficult to achieve the co-existence of ADTMs with nonmetal atoms and clarify their synergistic effect on the catalytic mechanism.
View Article and Find Full Text PDFChem Rec
December 2024
Department of Chemistry, Jagannath University, Dhaka, 1100, Bangladesh.
Nitrate (NO ) contamination from industrial, agricultural, and anthropogenic activities poses significant risks to human health and ecosystems. While traditional NO remediation methods are effective, they often generate secondary pollutants and incur high costs. Electrochemical NO reduction (ECNR) offers a sustainable alternative, converting NO into environmentally benign nitrogen (N) or valuable ammonia (NH).
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
South China University of Technology, School of Chemistry and Chemical Engineering, Wushan St., 510640, Guangzhou, CHINA.
Electroreduction of CO2 to CO represents a highly promising way for artificial carbon cycling, but obtaining high selectivity over a wide potential window remains a challenge due to the sluggish CO generation and diffusion kinetics. Here we report an integration of long-range P modified asymmetrical bismuth atomic site on an ordered macroporous carbon skeleton with mesoporous "wall" (MW-BiN3-POMC) for efficient electroreduction of CO2. In-depth in-situ investigations with theoretical computations reveal that the incorporation of long-range P atom is able to strengthen the orbital interaction between the C 2p of CO2 and Bi 6p, thereby establishing an electronic transport bridge for the activation of CO2 molecule.
View Article and Find Full Text PDFAdv Mater
December 2024
Tianjin Key Lab for Rare Earth Materials and Applications, Center for Rare Earth and Inorganic Functional Materials, School of Materials Science and Engineering, National Institute for Advanced Materials, Nankai University, Tianjin, 300350, China.
Currently, there are still obstacles to rationally designing the ligand fields to activate rare-earth (RE) elements with satisfactory intrinsic electrocatalytic reactivity. Herein, axial coordination strategies and nanostructure design are applied for the construction of La single atoms (La-Cl SAs/NHPC) with satisfactory oxygen reduction reaction (ORR) activity. The nontrivial LaNCl motifs configuration and the hierarchical porous carbon substrate that facilitates maximized metal atom utilization ensure high half-wave potential (0.
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