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. 2016 Jul 5;3(10):1600189.
doi: 10.1002/advs.201600189. eCollection 2016 Oct.

Visible and Near-Infrared Photothermal Catalyzed Hydrogenation of Gaseous CO2 over Nanostructured Pd@Nb2O5

Jia Jia  1 , Paul G O'Brien  2 , Le He  3 , Qiao Qiao  4 , Teng Fei  2 , Laura M Reyes  2 , Timothy E Burrow  2 , Yuchan Dong  2 , Kristine Liao  2 , Maria Varela  5 , Stephen J Pennycook  6 , Mohamad Hmadeh  7 , Amr S Helmy  8 , Nazir P Kherani  9 , Doug D Perovic  1 , Geoffrey A Ozin  2
Affiliations

Visible and Near-Infrared Photothermal Catalyzed Hydrogenation of Gaseous CO2 over Nanostructured Pd@Nb2O5

Jia Jia et al. Adv Sci (Weinh). .

Abstract

The reverse water gas shift (RWGS) reaction driven by Nb2O5 nanorod-supported Pd nanocrystals without external heating using visible and near infrared (NIR) light is demonstrated. By measuring the dependence of the RWGS reaction rates on the intensity and spectral power distribution of filtered light incident onto the nanostructured Pd@Nb2O5 catalyst, it is determined that the RWGS reaction is activated photothermally. That is the RWGS reaction is initiated by heat generated from thermalization of charge carriers in the Pd nanocrystals that are excited by interband and intraband absorption of visible and NIR light. Taking advantage of this photothermal effect, a visible and NIR responsive Pd@Nb2O5 hybrid catalyst that efficiently hydrogenates CO2 to CO at an impressive rate as high as 1.8 mmol gcat-1 h-1 is developed. The mechanism of this photothermal reaction involves H2 dissociation on Pd nanocrystals and subsequent spillover of H to the Nb2O5 nanorods whereupon adsorbed CO2 is hydrogenated to CO. This work represents a significant enhancement in our understanding of the underlying mechanism of photothermally driven CO2 reduction and will help guide the way toward the development of highly efficient catalysts that exploit the full solar spectrum to convert gas-phase CO2 to valuable chemicals and fuels.

Keywords: carbon dioxide; niobium oxide nanostructure; palladium catalysts; photothermal catalysis; solar fuels.

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Figures

Figure 1
Figure 1
Synthesis, morphology and structure of Nb3O7(OH) nanorods and Pd@Nb2O5 nanocrystal–nanorod samples. a) Scheme of the synthesis of Nb3O7(OH) and Pd@Nb2O5 nanorod samples. b) TEM images of Nb3O7(OH) nanorod sample. c) TEM images of Pd@Nb2O5 nanocrystal–nanorod sample.
Figure 2
Figure 2
a) HAADF image of a Pd nanocrystal decorated Nb2O5 nanorod. The cyan arrow indicates the [010] growth direction of the nanorod, and the dashed yellow rectangle marks the area where EELS elemental mapping was taken. Scale bar, 5 nm. b) Enlarged image showing nanocrystalline Pd viewed from its [112] direction. The d‐spacing of the (111) and (022) planes was measured. c) Inverse FFT by masking spots only contributed from Pd, as indicated in the inserted figure by the red circles. The inserted figure is the FFT of (a), showing an overlap of contributions from Pd and Nb2O5. d) EEL spectra from the Pd nanocrystal (red), Nb2O5 nanorod (cyan), and interface between the Pd and Nb2O5 (blue). The Pd M4,5‐edge and Pd M3‐edge are visible in the red spectrum; the Nb M3‐edge, Nb M2‐edge and O K‐edge are visible in the cyan spectrum; a superposition of these edges are exhibited in the blue spectrum. e) HAADF image taken while simultaneously collecting the EELS map. f) Fitting coefficient of Pd showing the spatial distribution of the Pd signal. g) Fitting coefficient of Nb2O5 showing the spatial distribution of the Nb2O5 signal.
Figure 3
Figure 3
a) Diffuse reflectance spectra of Nb3O7(OH), Nb2O5 and Pd@Nb2O5 films dispersed on a borosilicate filter. b) The band energy diagram of Nb2O5 in comparison with the work function of Pd.
Figure 4
Figure 4
Photothermal catalytic performance of the nanostructured Pd@Nb2O5 samples. a) CO production rates over Pd@Nb2O5 in the dark at room temperature (RT), under irradiation from a 300 W Xe lamp, and in the dark at a reaction temperature of 160 °C. b) Spectral irradiance incident onto the Pd@Nb2O5 catalyst with different cut‐off filters for batch reaction tests A through F. c) Spectral irradiance incident onto the Pd@Nb2O5 catalyst for batch reactions I through V. d) The RWGS reaction rates plotted as a function of absorbed power for the series of batch reactions A–F (red line) and I–V (black line).
Figure 5
Figure 5
a) RWGS reaction rate measured in the dark as a function of reaction temperature. b) The effective reaction temperature as a function of radiant power absorbed by the Pd@Nb2O5 catalyst. The equation used to estimate T e is provided in Figure b.
Figure 6
Figure 6
Possible reaction pathway for the reverse water gas shift reaction (RWGS) on the Pd@Nb2O5 hybrid catalyst.
Figure 7
Figure 7
Dependence of the Raman frequency for νNb=O stretching vibrations of a) Pd@Nb2O5 and b) Nb2O5 nanorods at different power levels. c) Estimated temperatures for Pd@Nb2O5 and Nb2O5 at different power levels.
Figure 8
Figure 8
Photothermal catalysis by nanostructured Pd@Nb2O5 (reduced) sample. a) Without exposure to air, the production rates of CO over Pd@Nb2O5 kept monotonically increasing from the first run to the fourth run. When the sample was exposed to air for 24 h, the production rate of the fifth run dropped to that of the first. b) Diffuse reflectance spectra and appearance of (i) pristine Pd@Nb2O5 and (ii) reduced Pd@Nb2O5 nanostructured films. c) Schematic illustration of in situ generation of reduced surface niobium sites and/or oxygen vacancies during photothermal reaction.
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