Melt-salt-assisted direct transformation of solid oxide into atomically dispersed FeN4 sites on nitrogen-doped porous carbon

Hu, Jinwen; Wu, Danyang; Zhu, Chao; Hao, Ce; Xin, Cuncun; Zhang, Jiangwei; Guo, Jingya; Li, Nannan; Zhang, Guifeng; Shi, Yantao

doi:10.1016/j.nanoen.2020.104670

Cited by 66 publications

(22 citation statements)

References 32 publications

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“…Interestingly, the prominent peak located around 4.24 Å can be attributed to the scattering path of Th–Th bond in fourth coordination shell in Th 2 @ I h (7)-C 80 . Noteworthy that due to the obvious attenuation in higher χ (R), the strength of Th–Th bond with long distance in fourth coordination is not as strong as the typical metallic bond like Fe–Fe bond in first coordination of Fe foil 45 . However, it still can be recognized since there is no scattering path signal of Th–C bond at this distance.…”

Section: Resultsmentioning

confidence: 99%

Characterization of a strong covalent Th3+–Th3+ bond inside an Ih(7)-C80 fullerene cage

et al. 2021

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The nature of the actinide-actinide bonds is of fundamental importance to understand the electronic structure of the 5f elements. It has attracted considerable theoretical attention, but little is known experimentally as the synthesis of these chemical bonds remains extremely challenging. Herein, we report a strong covalent Th-Th bond formed between two rarely accessible Th3+ ions, stabilized inside a fullerene cage nanocontainer as Th2@Ih(7)-C80. This compound is synthesized using the arc-discharge method and fully characterized using several techniques. The single-crystal X-Ray diffraction analysis determines that the two Th atoms are separated by 3.816 Å. Both experimental and quantum-chemical results show that the two Th atoms have formal charges of +3 and confirm the presence of a strong covalent Th-Th bond inside Ih(7)-C80. Moreover, density functional theory and ab initio multireference calculations suggest that the overlap between the 7s/6d hybrid thorium orbitals is so large that the bond still exists at Th-Th separations larger than 6 Å. This work demonstrates the authenticity of covalent actinide metal-metal bonds in a stable compound and deepens our fundamental understanding of f element metal bonds.

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Section: Resultsmentioning

confidence: 99%

Characterization of a strong covalent Th3+–Th3+ bond inside an Ih(7)-C80 fullerene cage

et al. 2021

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“…The molten salt-assisted strategy makes it possible to utilize ordinary metal oxides (such as Fe 2 O 3 and Co 2 O 3 ) and small organic molecules (such as adenine) as precursors to produce carbon-supported SAECs [71]. Firstly, the molten salt (ZnCl 2 and NaCl with a mass ratio of 1 : 1), adenine, and Fe 2 O 3 were ground by ball mill.…”

Section: 22mentioning

confidence: 99%

Recent Advances in Single-Atom Electrocatalysts for Oxygen Reduction Reaction

2020

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Oxygen reduction reaction (ORR) plays significant roles in electrochemical energy storage and conversion systems as well as clean synthesis of fine chemicals. However, the ORR process shows sluggish kinetics and requires platinum-group noble metal catalysts to accelerate the reaction. The high cost, rare reservation, and unsatisfied durability significantly impede large-scale commercialization of platinum-based catalysts. Single-atom electrocatalysts (SAECs) featuring with well-defined structure, high intrinsic activity, and maximum atom efficiency have emerged as a novel field in electrocatalytic science since it is promising to substitute expensive platinum-group noble metal catalysts. However, finely fabricating SAECs with uniform and highly dense active sites, fully maximizing the utilization efficiency of active sites, and maintaining the atomically isolated sites as single-atom centers under harsh electrocatalytic conditions remain urgent challenges. In this review, we summarized recent advances of SAECs in synthesis, characterization, oxygen reduction reaction (ORR) performance, and applications in ORR-related H2O2 production, metal-air batteries, and low-temperature fuel cells. Relevant progress on tailoring the coordination structure of isolated metal centers by doping other metals or ligands, enriching the concentration of single-atom sites by increasing metal loadings, and engineering the porosity and electronic structure of the support by optimizing the mass and electron transport are also reviewed. Moreover, general strategies to synthesize SAECs with high metal loadings on practical scale are highlighted, the deep learning algorithm for rational design of SAECs is introduced, and theoretical understanding of active-site structures of SAECs is discussed as well. Perspectives on future directions and remaining challenges of SAECs are presented.

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“…In contrast to molten salts, doping precursors cannot be washed off easily, leading to surface impurities that may affect the catalytic performance of host materials or blur our understanding of structure–activity relationships. [ 37,38 ]…”

Section: Introductionmentioning

confidence: 99%

Simultaneous Manipulation of Bulk Excitons and Surface Defects for Ultrastable and Highly Selective CO₂ Photoreduction

et al. 2021

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The objective of photocatalytic CO2 reduction (PCR) is to achieve high selectivity for a single energy‐bearing product with high efficiency and stability. The bulk configuration usually determines charge carrier kinetics, whereas surface atomic arrangement defines the PCR thermodynamic pathway. Concurrent engineering of bulk and surface structures is therefore crucial for achieving the goal of PCR. Herein, an ultrastable and highly selective PCR using homogeneously doped BiOCl nanosheets synthesized via an inventive molten strategy is presented. With B2O3 as both the molten salt and doping precursor, this new doping approach ensures boron (B) doping from the surface into the bulk with dual functionalities. Bulk B doping mitigates strong excitonic effects confined in 2D BiOCl by significantly reducing exciton binding energies, whereas surface‐doped B atoms reconstruct the BiOCl surface by extracting lattice hydroxyl groups, resulting in intimate B‐oxygen vacancy (B‐OV) associates. These exclusive B‐OV associates enable spontaneous CO2 activation, suppress competitive hydrogen evolution and promote the proton‐coupled electron transfer step by stabilizing *COOH for selective CO generation. As a result, the homogeneous B‐doped BiOCl nanosheets exhibit 98% selectivity for CO2‐to‐CO reduction under visible light, with an impressive rate of 83.64 µmol g−1 h−1 and ultrastability for long‐term testing of 120 h.

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Melt-salt-assisted direct transformation of solid oxide into atomically dispersed FeN4 sites on nitrogen-doped porous carbon

Cited by 66 publications

References 32 publications

Characterization of a strong covalent Th3+–Th3+ bond inside an Ih(7)-C80 fullerene cage

Characterization of a strong covalent Th3+–Th3+ bond inside an Ih(7)-C80 fullerene cage

Recent Advances in Single-Atom Electrocatalysts for Oxygen Reduction Reaction

Simultaneous Manipulation of Bulk Excitons and Surface Defects for Ultrastable and Highly Selective CO₂ Photoreduction

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Melt-salt-assisted direct transformation of solid oxide into atomically dispersed FeN4 sites on nitrogen-doped porous carbon

Cited by 66 publications

References 32 publications

Characterization of a strong covalent Th3+–Th3+ bond inside an Ih(7)-C80 fullerene cage

Characterization of a strong covalent Th3+–Th3+ bond inside an Ih(7)-C80 fullerene cage

Recent Advances in Single-Atom Electrocatalysts for Oxygen Reduction Reaction

Simultaneous Manipulation of Bulk Excitons and Surface Defects for Ultrastable and Highly Selective CO2 Photoreduction

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Product

Resources

About

Simultaneous Manipulation of Bulk Excitons and Surface Defects for Ultrastable and Highly Selective CO₂ Photoreduction