Herein we report the electrocatalytic activity of boron-doped graphene for the reduction of CO2. Electrolysis takes place at low overpotentials leading exclusively to formate as the product (vis-à-vis benchmark Bi catalyst). Computational studies reveal mechanistic details of CO2 adsorption and subsequent conversion to formic acid/formate.

Enhancing the intrinsic activity of a benchmarked electrocatalyst such as platinum (Pt) is highly intriguing from fundamental as well as applied perspectives. In this work, hydrogen evolution reaction (HER) activity of Pt electrodes, benchmarked HER catalysts, modified with ultrathin sheets of hexagonal boron nitride (h-BN) is studied in acidic medium (Pt/h-BN), and augmented HER performance, in terms of the overpotential at a 10 mA cm–2 current density (10 mV lower than that of Pt nanoparticles) and a lower Tafel slope (29 ± 1 mV/decade), of the Pt/h-BN system is demonstrated. The effects of h-BN surface modification of bulk Pt as well as Pt nanoparticles are studied, and the origin of such an enhanced HER activity is probed using density functional theory-based calculations. The HER charge transfer resistance of h-BN-modified Pt is found to be drastically reduced, and this enhances the charge transfer kinetics of the Pt/h-BN system because of the synergistic interaction between h-BN and Pt. An enormous reduction in the hydrogen adsorption energy on h-BN monolayers is also found when they are placed over the Pt electrode [−2.51 eV (h-BN) to −0.25 eV (h-BN over Pt)]. Corrosion preventive atomic layers such as h-BN-protected Pt electrodes that perform better than Pt electrodes do open possibilities of benchmarked catalysts by simple modification of a surface via atomic layers.

A single material that can perform water oxidation and oxygen reduction reactions (ORR), also called bifunctional catalyst, represents a novel concept that emerged from recent materials research and that has led to applications in new‐generation energy‐storage systems, such as regenerative fuel cells. Here, metal/metal‐oxide free, doped graphene derived from rhombohedral boron carbide (B4C) is demonstrated to be an effective bifunctional catalyst for the first time. B4C, one of the hardest materials in nature next to diamond and cubic boron nitride, is converted and separated in bulk to form heteroatom (boron, B) doped graphene (BG, yield ≈7% by weight, after the first cycle). This structural conversion of B4C to graphene is accompanied by in situ boron doping and results in the formation of an electrochemically active material from a non‐electrochemically active material, broadening its potential for application in various energy‐related technologies. The electrocatalytic efficacy of BG is studied using various voltammetric techniques. The results show a four‐electron transfer mechanism as well as a high methanol tolerance and stability towards ORR. The results are comparable to those from commercial 20 wt% Pt/C in terms of performance. Furthermore, the bifunctionality of the BG is also demonstrated by its performance in water oxidation.

Although graphene technology has reached technology readiness level 9 and hydrogen fuel has been identified as a viable futuristic energy resource, pristine atomic layers such as graphene are found to be inactive towards the hydrogen evolution reaction (HER). Enhancing the intrinsic catalytic activity of a material and increasing its number of active sites by nanostructuring are two strategies in novel catalyst development. Here, electrocatalytically inert graphene (G) and hexagonal boron nitride (hBN) are made active for the HER by forming van der Waals (vdW) heterostructures via vertical stacking. The HER studies are conducted using defect free shear exfoliated graphite and hBN modified glassy carbon electrodes via layer by layer sequential stacking. The G/hBN stacking pattern (AA, AB, and AB') and stacking sequence (G/hBN or hBN/G) have been found to play important roles in the HER activity. Enhancement in the intrinsic activity of graphene by the formation of G/hBN vdW stacks has been further confirmed with thermally reduced graphene oxide and hBN based structures. Tunability in the HER performance of the G/hBN vdW stack is also confirmed via a three-dimensional rGO/hBN electrode. HER active sites in the G/hBN vdW structures are then mapped using density functional theory calculations, and an atomistic interpretation has been identified.