Light-Enhanced Carbon Dioxide Activation and Conversion by Effective Plasmonic Coupling Effect of Pt and Au Nanoparticles

Abstract

Photocatalytic reduction of carbon dioxide (CO) is attractive for the production of valuable fuels and mitigating the influence of greenhouse gas emission. However, the extreme inertness of CO and the sluggish kinetics of photoexcited charge carrier transfer process greatly limit the conversion efficiency of CO photoreduction. Herein, we report that the plasmonic coupling effect of Pt and Au nanoparticles (NPs) profoundly enhances the efficiency of CO reduction through dry reforming of methane reaction assisted by light illumination, reducing activation energies for CO reduction ∼30% below thermal activation energies and achieving a reaction rate 2.4 times higher than that of the thermocatalytic reaction. UV-visible (vis) absorption spectra and wavelength-dependent performances show that not only UV but also visible light play important roles in promoting CO reduction due to effective localized surface plasmon resonance (LSPR) coupling between Pt and Au NPs. Finite-difference time-domain simulations and in situ diffuse reflectance infrared Fourier transform spectroscopy further reveal that effective coupling LSPR effect generates strong local electric fields and excites high concentration of hot electrons to activate the reactants and intermediate species, reduce the activation energies, and increase the reaction rate. This work provides a new pathway toward the efficient plasmon-enhanced chemical reactions via reducing the activation energies by utilizing solar energy.

Advances in catalytic conversion of methane and carbon dioxide to highly valuable products

“…Solar energy would be a solution for the energy issue. Therefore, photocatalysis was exploited to break this thermodynamic limitation and to solve the issue of large energy requirement . Shimura and Yoshida explored Ga 2 O 3 as a photocatalyst for CH 4 and CO 2 at lower temperature .…”

“…,[286][287][288][289][290][291][292] Shimura and Yoshida explored Ga 2 O 3 as a photocatalyst for CH4 and CO 2 at lower temperature 289. They found that, under UV irradiation, DRM could not occur at temperature below 200°C.…”

Thermo‐Photocatalysis: Environmental and Energy Applications

“…The high NIR absorptiono ft he photocatalyst is attributed to oxygen vacancies in the Bi 2 WO 6 structure. [22,23] Oxides, sulfides, and, particularly,m etal-based materials are used in this context. Another strategy is to prepare nanocomposites of UV or visible photocatalystsw ithd ifferent materials (e.g.,r are earth metal ions, carbon quantum dots) that convert IR light to UV or Vis light.…”

“…Another strategy is to prepare nanocomposites of UV or visible photocatalystsw ithd ifferent materials (e.g.,r are earth metal ions, carbon quantum dots) that convert IR light to UV or Vis light. [22] for more details). The generated e À and h + can then participate in atypical photocatalytic reaction.…”

“…A) Schematic representation of UV/Vis/IR degradation of methyl orange by using Bi 2 WO 6 /TiO 2 nanobelts(inset: TEM view). [22].Copyright 2018A merican Chemical Society. [19].Copyright 2010 Wiley-VCH.…”