Dual Photocatalytic Roles of Light: Charge Separation at the Band Gap and Heat via Localized Surface Plasmon Resonance To Convert CO₂ into CO over Silver–Zirconium Oxide

Abstract

Confirmation of 13CO2 photoconversion into a 13C-product is crucial to produce solar fuel. However, the total reactant and charge flow during the reaction is complex; therefore, the role of light during this reaction needs clarification. Here, we chose Ag–ZrO2 photocatalysts because beginning from adventitious C, negligible products are formed using them. The reactants, products, and intermediates at the surface were monitored via gas chromatography–mass spectrometry and FTIR, whereas the temperature of Ag was monitored via Debye–Waller factor obtained by in situ extended X-ray absorption fine structure. With exposure to 13CO2, H2, and UV–visible light, 13CO selectively formed, while 8.6% of the 12CO mixed in the product due to the formation of 12C-bicarbonate species from air that exchanged with the 13CO2 gas-phase during a 2 h reaction. By choosing the light activation wavelength, the CO2 photoconversion contribution ratio was charge separated at the ZrO2 band gap (λ < 248 nm): 70%, localized at the Ag surface plasmon resonance (LSPR) (330 < λ < 580 nm): 28%, and characterized by a thermal energy of 295 K: 2%. LSPR at the Ag surface was converted to heat at temperatures of up to 392 K, which provided an efficient supply of activated H species to the bicarbonate species, combined with separated electrons and holes above the ZrO2, which generated CO at a rate of 0.66 μmol h–1 gcat –1 with approximately zero order kinetics. Photoconversion of 13CO2 using moisture was also possible. Water photo-oxidation step above ZrO2 was rate-limited, and the side reactions that formed H2 above the Ag were successfully suppressed instead to produce CO via the Mg2+ addition to trap CO2 at the surface.

Cobalt Plasmonic Superstructures Enable Almost 100% Broadband Photon Efficient CO2 Photocatalysis

“…This peak was significantly suppressed after 10‐min light irradiation, indicating the increased Debye–Waller factor (σ) value and the increased temperature (Figure 5; Figure S21 and Table S2, Supporting Information). [ 18 ] By contrast, the EXAFS spectrum of Co@SiO 2 exhibited a less obvious drop of the peak intensity after turning on the light, which was an indication of its lower local temperature under the illumination (Figure 5b). Moreover, the peak intensity returned to the original state for both samples after turning off the light, which was consistent with the light‐induced increase of local temperature of catalysts.…”

“…As suggested in a recent study, the increased Debye–Waller factor typically showed a decreased peak intensity in the EXAFS spectrum. [ 18 ] A main peak at 2.2 Å corresponding to metallic CoCo bonds was observed in the EXAFS spectrum of Co‐PS@SiO 2 ( Figure a). This peak was significantly suppressed after 10‐min light irradiation, indicating the increased Debye–Waller factor (σ) value and the increased temperature (Figure 5; Figure S21 and Table S2, Supporting Information).…”

Plasmonic Photocatalysts for Sunlight‐Driven Reduction of CO2: Details, Developments, and Perspectives

“…The LSPR of Ag PNPs can create a local heat that assists the CO 2 photoreduction. Zhang and colleagues showed that, for CO 2 photoreduction in the presence of H 2 on Ag‐loaded ZrO 2 (Ag–ZrO 2 ) as photocatalyst, the local heat created by the LSPR of Ag NPs effectively activated H 2 to form H species, which were supplied to the CO 2 reduction on ZrO 2 surface sites . CO was efficiently generated at a rate of 0.66 μmol g −1 h −1 with approximately zero‐order kinetics.…”

Investigation of copper oxidation states in plasmonic nanomaterials by XAS and Raman spectroscopy

“…thermal, "hot electron" or redox). [2][3][4][5][6][7] The mechanism of the Ullmann reaction is a subject of much debate, and different mechanisms have been proposed in the literature, depending on whether the catalysis is heterogeneous or homogeneous, and whether assisted by light. [8][9][10][11][12][13][14][15] The most commonly described mechanisms for this reaction are a classical catalytic oxidation pathway and reductive elimination, or a radical pathway.…”