Linking Bi-Metal Distribution Patterns in Porous Carbon Nitride Fullerene to Its Catalytic Activity toward Gas Adsorption

Abstract

Immobilization of two single transition metal (TM) atoms on a substrate host opens numerous possibilities for catalyst design. If the substrate contains more than one vacancy site, the combination of TMs along with their distribution patterns becomes a design parameter potentially complementary to the substrate itself and the bi-metal composition. By means of DFT calculations, we modeled three dissimilar bi-metal atoms (Ti, Mn, and Cu) doped into the six porphyrin-like cavities of porous C24N24 fullerene, considering different bi-metal distribution patterns for each binary complex, viz. TixCuz@C24N24, TixMny@C24N24, and MnyCuz@C24N24 (with x, y, z = 0–6). We elucidate whether controlling the distribution of bi-metal atoms into the C24N24 cavities can alter their catalytic activity toward CO2, NO2, H2, and N2 gas capture. Interestingly, Ti2Mn4@C24N24 and Ti2Cu4@C24N24 complexes showed the highest activity and selectively toward gas capture. Our findings provide useful information for further design of novel few-atom carbon-nitride-based catalysts.

Distribution Pattern of Metal Atoms in Bimetal-Doped Pyridinic–N4 Pores Determines Their Potential for Electrocatalytic N2 Reduction

“…The charge density difference (CDD) map is provided in Figure 1b. Thus, as demonstrated here and in our previous report, 62 the TM-anchored C 24 N 24 substrate is stable enough to effectively catalyze NRR.…”

“…Recently, TM-doped C 24 N 24 and C 24 B 24 fullerenes were studied for hydrogen storage, 58−60 ORR, 61 and gas conversion. 55 In our previous study, 62 we investigated the effects of various distribution patterns of two different TM atoms in six N 4 cavities of a C 24 N 24 cage (Ti x Cu z @C 24 N 24 , Ti x Mn y @C 24 N 24 , and Cu z Mn y @C 24 N 24 , x, y, z = 0−6) on their geometric, thermodynamic, and electronic properties. Also, we investigated the selectivity of doped atoms toward gas adsorption (N 2 , CO 2 , H 2 , and NO 2 ).…”