Boosting ORR/OER Activity of Graphdiyne by Simple Heteroatom Doping

Abstract

Nitrogen‐doped graphdiynes recently emerged as promising metal‐free oxygen reduction reaction (ORR) electrocatalysts. However, which type of N‐dopants contributing to the enhanced catalytic performance and the catalytic performances of other heteroatom‐doped graphdiynes has not been explored systematically. Herein, ORR and oxygen evolution reaction (OER) catalytic performances of X‐doped graphdiynes are examined by means of DFT computations (X = B, N, P, and S). It is revealed that the graphitic S‐doped graphdiyne (Model S1), the sp‐N‐doped graphdiyne (Model N3) and the graphitic P‐doped graphdiyne (Model P1) exhibit comparable or even better ORR/OER activities than Pt/C or RuO2, with ORR activity trend as Model S1 > Pt/C > Model N3 and OER trend as Model P1 > RuO2 > Model N3. The carbon atoms near N‐ and S‐dopants and featuring large positive charge are the ORR active sites in Models N3 and S1, whereas the carbon atoms near N‐ and P‐dopants and possessing high spin are the OER active sites in Models N3 and P1. Overall, this study not only gains deep insights into the catalytic activity of N‐doped graphdiyne for ORR, but also guides developing of graphdiyne‐based ORR/OER catalysts beyond N‐doping.

Probing the active sites of site-specific nitrogen doping in metal-free graphdiyne for electrochemical oxygen reduction reactions

“…6a). According to the adjusted R square (R 2 ) of the fitted equations, the linear relationship between DG(OOH*) and DG (OH*) is better than that between DG(O*) and DG(OH*) [70,71]. Based on the scaling relations between DG(OOH*), DG(O*) and DG (OH*) fitted in Fig.…”

A Disquisition on the Active Sites of Heterogeneous Catalysts for Electrochemical Reduction of CO2 to Value‐Added Chemicals and Fuel

“…[191] The introduction of oxygen vacancies increases the charge density of ZnO resulting in the enhanced CO generation with j and maximum FE of −16.1 mA cm −2 and 83%, respectively at −1.1 V. Recently, oxygen vacancies on Cu-based catalysts can be tuned toward electrocatalytic CO 2 reduction to generate ethylene and ethanol. [192,193] Gu et al reported that partially reduced Cu oxide nanodendrites with surface-rich oxygen vacancies serving as excellent Lewis base sites for enhanced adsorption of *CO 2 and the release of *CH 2 which were further hydrogenated to form ethylene. [192] The maximum FE C2H4 and its corresponding partial j are 63% and −18.5 mA cm −2 , respectively at operating potential of −1.4 V. Similarly, we also proposed a strategy to produce a unique Adv.…”

“…[192,193] Gu et al reported that partially reduced Cu oxide nanodendrites with surface-rich oxygen vacancies serving as excellent Lewis base sites for enhanced adsorption of *CO 2 and the release of *CH 2 which were further hydrogenated to form ethylene. [192] The maximum FE C2H4 and its corresponding partial j are 63% and −18.5 mA cm −2 , respectively at operating potential of −1.4 V. Similarly, we also proposed a strategy to produce a unique Adv. Energy Mater.…”

“…Data from refs. [147,[191][192][193][194][195][196][197][198]. The detailed catalytic activity of these catalysts is presented in Table S3 (Supporting Information).…”

Atomic-Level Functionalized Graphdiyne for Electrocatalysis Applications

“…To date, N-doped graphite carbon material including activated carbon, carbon nanotubes and graphene [72,[101][102][103] have demonstrated to be the effective ORR catalysts. In this respect, the ORR process of N-atom-doped GDY on the cathode of a fuel cell was also discussed in many studies [104][105][106][107][108][109][110][111]. The ORR mechanism of N-doped GDY was investigated by using the first principles calculations.…”