Single Vanadium Atoms Anchored on Graphitic Carbon Nitride as a High-Performance Catalyst for Non-oxidative Propane Dehydrogenation

Abstract

In comparison with oil-based cracking technologies, the on-purpose dehydrogenation of propane (PDH) is a more eco-friendly and profitable approach to produce propylene. By means of density functional theory calculations, the present work reveals that the single vanadium (V) atom anchored on graphitic carbon nitride (V1/g-C3N4) may serve as a promising single-atom catalyst for non-oxidative PDH with industrially practical activity, selectivity, and thermal stability. The high activity of V1/g-C3N4 for PDH is attributed to the low-coordinated 3d orbitals of single V atoms, while the propylene selectivity is originated from the inhibition of the di-σ binding mode of propylene on the single V atoms. This work provides a guideline to design and screen out promising single-atom catalysts for selective dehydrogenation of alkanes.

Molecular Engineering toward Pyrrolic N‐Rich M‐N4 (M = Cr, Mn, Fe, Co, Cu) Single‐Atom Sites for Enhanced Heterogeneous Fenton‐Like Reaction

“…The fast and efficient redox cycles of Cr 3+ / Cr 2+ further promote the electron transfer and the exposure of more Cr(II)-N 4 reactive sites for H 2 O 2 activation in the HFLR. Moreover, this metalloporphyrin-like Cr-N 4 sites are very stable, which leads to an unprecedented wide working pH range (3)(4)(5)(6)(7)(8)(9)(10)(11) and remarkable durability and reusability of the SA-Cr/ PN-g-C 3 N 4 for HFLR. Also, this coupled system will minimize the consumption of H 2 O 2 and metallic catalysts due to the production of extra reactive species by photocatalysis and the utmost utilization of metallic catalytic sites of the SACs.…”

“…Single‐atom catalysts (SACs) bridge the gap between homogeneous catalysis and heterogeneous catalysis and maximize the atomic utilization efficiency of transition and noble metals. [ 1,2 ] SACs on support surfaces possess unique chemical and physical properties, fine‐tuned active sites, and outstanding activity, selectivity and durability, [ 3–5 ] which are different from the conventional catalysts from sub‐nanoscale to microscale. However, with the decrease of particle size, metal catalysts tend to self‐aggregate into clusters or particles because of the dramatically increased surface energy.…”

The systematical detection and structure characterization of vanadium‐oxygen species in low concentration solutions by surface‐enhanced Raman spectroscopy experiments and density functional theory calculations

“…DFT calculation can be conducted by different level of theory, and B3LYP/6‐31G level is the effective method to predicate the properties of small nonmetals such as oxygen and metals such as vanadium. [ 40–44 ] The input files of each vanadium–oxygen species for the DFT calculation are shown in Supporting Information.…”

Single‐Atom Catalysts: A Sustainable Pathway for the Advanced Catalytic Applications

“…[197] Kong et al theoretically confirmed that vanadium atoms were anchored on graphitic carbon nitride for nonoxidative propane dehydrogenation. [346] The high activity of V 1 /g-C 3 N 4 was attributed to low coordination 3d orbital of V atoms, while propylene selectivity was initiated from inhibition of di-σ binding mode of propylene on single V atoms.…”