A series of 27 composite structures, consisting of superhalogen and Brønsted acid, is designed and systematically studied based on combined ab initio and DFT calculations focusing on their potentials as novel superacids. As indicated by high-level CCSD(T) results, all the composites here fulfill the theoretical criterion for superacid and the acidities of two of them are close to the strongest superacid ever reported. The influences of various factors on the superacid properties of these composites were analyzed in detail. Our results demonstrate that the acidity of these superacids is mainly determined by the superhalogen components while the effect of Brønsted acids, irrespective of their number or type, is relatively mild. Therefore, it is probable to design novel composite superacid with enhanced property through the regulation of the superhalogen component. It is encouraging that MP2 and DFT could also provide reliable results when compared with the high-level CCSD(T) method. The reliability of these low-cost methods implies the capability of theoretical calculations for future composite superacid of enlarged size, and thus it is highly probable that an effective guide to the related experimental research could be provided by the theory.

Recently, carbon nanomaterials doped with nonmetallic atoms have been used as electrocatalysts involved in oxygen reduction reactions (ORRs) because of the lack of degradation and contamination problems caused by metal dissolution, low cost, sustainability, and multifunctionality. In this study, the metal-free N-, P-, O-tridoped carbon hollow nanospheres (N, P, O-Carbon) with openings in the shell surfaces have been developed, where poly­(o-phenylenediamine) hollow nanospheres with openings in the shell surfaces were chosen as a nitrogen-rich polymer, and then different phosphorus sources (such as NaH2PO2, H3PO4, and phytic acid (PA)) were introduced for heat treatment. When used as electrocatalysts, N, P, O-Carbon-PA showed the best ORR electroactivity with an onset potential (E onset ) of 0.98 V and the limit current density of 5.39 mA cm–2. The origin of high activity associated with heteroatom doping was elucidated by X-ray photoelectron spectroscopy and density functional theory. The results evidenced the high potential of N, P, O-Carbon as highly active nonmetal ORR electrocatalysts. It can be expected that the conclusions rendered herein will provide guidance for the reasonable design of other heteroatom-doped carbon for wider applications.

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A fundamental understanding of metal active sites in single‐atom catalysts (SACs) is important and challenging in the development of high‐performance catalyst systems. Here, a highly efficient and straightforward molten‐salt‐assisted approach is reported to create atomically dispersed cobalt atoms supported over vanadium pentoxide layered material, with each cobalt atom coordinated with four neighboring oxygen atoms. The liquid environment and the strong polarizing force of the molten salt at high temperatures potentially favor the weakening of VO bonding and the formation of CoO bonding on the vanadium oxide surface. This cobalt SAC achieves extraordinary catalytic efficiency in acceptorless dehydrogenative coupling of alcohols with amines to give imines, with more than 99% selectivity under almost 100% conversion within 3 h, along with a high turnover frequency (TOF) of 5882 h−1, exceeding those of previously reported benchmarking catalysts. Moreover, it delivers excellent recyclability, reaction scalability, and substrate tolerance. Density functional theory (DFT) calculations further confirm that the optimized coordination environment and strong electronic metal‐support interaction contribute significantly to the activation of reactants. The findings provide a feasible route to construct SACs at the atomic level for use in organic transformations.

The construction route of organic superacids from the combination of organic superhalogens and protons is verified to be a rational one based on a systematic theoretical study covering different planar conjugated backbones, e.g., [C5H5]− and [BC5H6]−, and electron-withdrawing substituents, e.g., –F, –CN and –NO2.