Single-Electron Activation of CO₂ on Graphene-Supported ZnO Nanoclusters: Effects of Doping in the Support

Abstract

Use of solar energy to convert the greenhouse gas CO2 into useful chemicals or fuels could not only reduce the accumulation of CO2 in the atmosphere but also provide a solution to sustainable energy development. There has been much interest in understanding the mechanistic role of graphene when added to semiconductor nanostructures to reduce CO2 because of the observation of enhanced photocatalytic activities in recent experiments. In this work, we investigate the adsorption and single-electron activation of CO2 on ZnO nanoclusters with and without a modified graphene support using a first-principles approach, with a special focus on the effect of the support. The formation of the CO2 – anion is identified under simulated photoexcitation conditions and is energetically more favorable than for previously studied oxide photocatalysts. The calculated results suggest that single-heteroatom doping in graphene has a significant impact on the catalytic activity of ZnO. The electronic coupling between the support and the semiconductor cluster plays a critical role in the activation of CO2 on the supported ZnO cluster. n-type doping helps to retain the photoexcited electron on ZnO and facilitates CO2 reduction on ZnO, whereas p-type doping enhances charge transfer from the photoexcited ZnO to graphene and would be useful for reductions occurring on graphene.

Heterostructure of ZnO Nanosheets/Zn with a Highly Enhanced Edge Surface for Efficient CO2 Electrochemical Reduction to CO

“…Furthermore, the surface atomic arrangement on the (11̅ 00) plane is reported, where the distance of two Zn atoms is much closer than that of the (0001) plane, which provides good sites for the stabilization of the *CO 2 − anion. 32 Therefore, the enhancement of CO production could be explained by more exposed (11̅ 00) edge sites on the ZnO sheet array/Zn, which originated from the facilitated CO 2 activation.…”

Cobalt Carbide from Co–Mn Layered Double Hydroxide: Highly Efficient Catalyst for Toluene Pyrolysis

“…22,38,39 To depict the valence orbitals of atoms, the double numeric plus polarization (DNP) basis set was implemented in the local atomic orbital basis set with a global orbital cutoff of 4.5 Å. 40,41 The tolerance of the energy was set to be 1 × 10 −6 eV per cell. Fine quality calculations were adopted during the geometry optimization, while 2 × 2 × 1 k-points were set for the calculations.…”

“…This is to theoretically find the adsorption of toluene on the crystal plane of Co 2 C, where the spin-polarized density functional dispersion correction (DFT-D) calculations were performed with the Dmol 3 package of the Materials Studio software package (Accelrys Software Inc., San Diego, CA) throughout the whole calculations. The exchange–correlation potential was optimized by the plane-wave sets of the generalized-gradient approximation using the form of the functional proposed by Perdew, Burke, and Ernzerhof (GGA-PBE). ,, To depict the valence orbitals of atoms, the double numeric plus polarization (DNP) basis set was implemented in the local atomic orbital basis set with a global orbital cutoff of 4.5 Å. , The tolerance of the energy was set to be 1 × 10 –6 eV per cell. Fine quality calculations were adopted during the geometry optimization, while 2 × 2 × 1 k -points were set for the calculations.…”

Recent Progresses in Constructing the Highly Efficient Ni Based Catalysts With Advanced Low-Temperature Activity Toward CO2 Methanation

“…Secondly, the novel support can endow the metallic active center in high dispersion state. For example, the graphene oxide can modify the electronic structure of Ni on the catalyst surface and reduce the dissociation energy of H 2 and CO 2 (He et al, 2016). Ma et al (2019) prepared Ni-SiO 2 /GO-Ni-foam catalyst by intercalation method.…”