Di Zhang

Developing single-atom catalysts with porous micro-/nanostructures for high active-site accessibility is of great significance but still remains a challenge. Herein, we for the first time report a novel template-free preassembly strategy to fabricate porous hollow graphitic carbonitride spheres with single Cu atoms mounted via thermal polymerization of supramolecular preassemblies composed of a melamine–Cu complex and cyanuric acid. Atomically dispersed Cu–N3 moieties were unambiguously confirmed by spherical aberration correction electron microscopy and extended X-ray absorption fine structure spectroscopy. More importantly, this material exhibits outstanding catalytic performance for selective oxidation of benzene to phenol at room temperature, especially showing phenol selectivity (90.6 vs 64.2%) and stability much higher than those of the supported Cu nanoparticles alone, originating from the isolated unique Cu–N3 sites in the porous hollow structure. An 86% conversion of benzene, with an unexpectedly high phenol selectivity of 96.7% at 60 °C for 12 h, has been achieved, suggesting a great potential for practical applications. This work paves a new way to fabricate a variety of single-atom catalysts with diverse graphitic carbonitride architectures.

With the aid of direct numerical simulation, this paper presents a detailed investigation on the flow around a finite square cylinder at a fixed aspect ratio (AR) of 4 and six Reynolds numbers (Re = 50, 100, 150, 250, 500, and 1000). It is found that the mean streamwise vortex structure is also affected by Re, apart from the AR value. Three types of mean streamwise vortices have been identified and analyzed in detail, namely, “Quadrupole Type” at Re = 50 and Re = 100, “Six-Vortices Type” at Re = 150 and Re = 250, and “Dipole Type” at Re = 500 and Re = 1000. It is the first time that the “Six-Vortices Type” mean streamwise vortices are reported, which is considered as a transitional structure between the other two types. Besides, three kinds of spanwise vortex-shedding models have been observed in this study, namely, “Hairpin Vortex Model” at Re = 150, “C and Reverse-C and Hairpin Vortex Model (Symmetric Shedding)” at Re = 250, and “C and Reverse-C and Hairpin Vortex Model (Symmetric/Antisymmetric Shedding)” at Re = 500 and Re = 1000. The newly proposed “C and Reverse-C and Hairpin Vortex Model” shares some similarities with “Wang’s Model” [H. F. Wang and Y. Zhou, “The finite-length square cylinder near wake,” J. Fluid Mech. 638, 453–490 (2009)] but differs in aspects such as the absence of the connection line near the free-end and the “C-Shape” vortex structure in the early stage of the formation of the spanwise vortex.