Black Nano Titania for Efficient Solar Energy Utilization

doi:10.7503/cjcu20150741

Abstract

Abstract:

Insufficient visible-light power conversion has been a great challenge for nanotitania photocatalysts in solar energy utilization.Recently, a new material—black TiO₂ has attracted enormous attention due to its greatly enhanced solar absorption and photocatalytic activity. Our group has made tremendous contributions to the researches of black TiO₂ via developing many effective preparation methods harvesting the extremely efficient black titania. Herein lie our recent progresses in researching black nanotitania, and a special emphasis on the fabrication methods, the chemical/physical properties and solar application.

Key words: Black titania, Visible solar light, Photocatalysis

CLC Number:

O643

TrendMD:

ZHU Guilian, LIN Tianquan, HUANG Fuqiang. Black Nano Titania for Efficient Solar Energy Utilization[J]. Chem. J. Chinese Universities, 2015, 36(11): 2099.

Figures/Tables 17

Fig.1 Diffuse reflectance spectra of H-doped black titania(TiO2-xHx) and pristine TiO2(P25, starting material)[26] The backgroud is the total solar spectrum. Copyright from Wiley-VCH.

Fig.2 HRTEM micrograph of black TiO2-xHx(A), EPR spectrum(B), Ti2p XPS spectra(C) and photoluminescent spectra(D) of black TiO2-xHx and prisitine TiO2[26] Copyright from Wiley-VCH.

Fig.3 Schematic low-temperature reduction of TiO2 in a two-zone furnace(A), Ellingham diagram of ΔG vs. temperature(B), photographs of pristine TiO2, gray TiO2-x obtained by H2 anneal(H2-TiO2-x), and black TiO2-x obtained by Al reduction(Al-TiO2-x)(C), mass production of black titania(TiO2-x) using our Al-reduction method(D) and absorption spectra of TiO2-x samples reduced at different temperatures, the H2 annealed H2-TiO2-x and high-pressure hydrogenated black titania(HP-TiO2, from ref.[12])(D)[27] Copyright from the Royal Society of Chemistry.

Fig.4 HRTEM images of TiO2 nanocrystals before(A) and after(B—D) Al reduction at different temperatures for 6 h, Raman spectra(E), EPR spectra of black TiO2-x and pristine TiO2 as a reference sample(F), Ti2p XPS spectra(G) and XPS valence band spectra(H) of pristine TiO2 and TiO2-x[27] Copyright from the Royal Society of Chemistry.

Fig.5 SEM(A), HRTEM images of TiO2-Al(B), UV-Vis absorption spectra(C), XRD patterns(D), Raman spectra(E) and EPR spectra(F) of TiO2-Al and TiO2-air nanowires[37] Copyright from Wiley-VCH.

Fig.6 Absorption spectra and photographs(inset) of as-TNTs, TNTs, and B-TNTs(A), typical top view FE-SEM of B-TNTs(B), sideview FE-SEM of B-TNTs(inset is the full side view)(C), typical top view of B-TNTS(D), XRD patterns(E) and Raman spectra of TNTs with different annealing treatment(inset is the magnification of Eg peak)(F), Ti2p XPS(G) and XPS valence band spectra(H) of TNTs and B-TNTs[29]

Fig.7 XRD patterns of pristine TiO2 and black TiO2-x after Al reduction at different temperatures for 4 h(A), SEM images of synthesized TiO2(B), HRTEM images of TiO2(C), T500(D), UV-Vis-NIR diffuse reflectance(E) and EPR spectra(F) of the pristine TiO2 and the TiO2-x after Al reduction at different temperatures for 4 h[32] Copyright from the Royal Society of Chemistry.

Fig.8 Diffuse reflectance spectra of SrTiO3 and reduced SrTiO3 samples[40] Copyright from the Royal Society of Chemistry.

Fig.9 Schematic core/shell structures of TiO2@TiO2-x(denoted as TiO2-x) and TiO2@TiO2-X(denoted as TiO2-X) with Ti4+(oxygen vacancies and X sites in green, white and orange, respectively)(A), HRTEM image of black TiO2-x nanocrystals(B) and diffuse reflectance spectra of TiO2-X(X=H, N, S, I) and solar spectral irradiance(right)(C)[30] Copyright from the Royal Society of Chemistry.

Fig.10 High resolution XPS spectra of N1s and Ti2p of TiO2-N(A, B), S2pXPS spectrum of TiO2-S(C), I3d XPS spectrum acquired from TiO2-I(D), EPR spectra(E) and PL spectra(F) of TiO2-x, TiO2-I, TiO2-N, TiO2-S and pristine TiO2[30] Copyright from the Royal Society of Chemistry.

Fig.11 Schematic synthetic route of rutile TiO2 with sulfided surface(R'-TiO2-S)(A), diffuse reflectance spectra of R-TiO2, R-TiO2-S and R'-TiO2-S with different sulfidation time(B), S2p XPS spectra of R'-TiO2-S and R-TiO2(C), EPR spectra of R'-TiO2-S, A-TiO2-x and pristine A-TiO2(D) and photoluminescent spectra of R'-TiO2-S and R-TiO2(E)[28] Copyright from the American Chemical Society.

Fig.12 HRTEM image of T400(A), UV-Vis absorption spectra(B), EPR spectra(C), Raman spectra(D), 1H NMR spectra(E) and PL spectra(F) of reference P25 and the reduced samples[31] The insets in (D) and (E) are partial magnification of the marked region with a red border. Copyright from Wiley-VCH.

Fig.13 Evaluation of the photocatalytic activities of TiO2-x[27] (A) UV light photo-catalytic degradation of methyl orange; (B) visible light photocatalytic degradation of methyl orange; (C) H2 generation of black TiO2-x under UV light; (D) visible light irradiation. Copyright from the Royal Society of Chemistry.

Fig.15 Photoelectrochemical properties of R'-TiO2-S, R-TiO2-S, TiO2-S, and R-TiO2 electrodes (A) Chopped J-V curves under simulated solar light illumination; (B) visible-light illumination via a three-electrode setup(TiO2 working, Pt counter, Ag/AgCl reference electrode, scan rate of 10 mV/s) in 1 mol/L NaOH electrolyte(pH=13.6); (C) photoconversion efficiencies as a function of applied potential; (D) IPCE spectra in the region of 300—700 nm at 0.65 VRHE. Inset of (D) IPCE spectra in the region of 420—700 nm[28]. Copyright from the American Chemical Society.

Fig.16 Thermal image map of cool-pressed disks after irradiation under AM 1.5 G Xe lamp solar simulator for different time[27] Copyright from the Royal Society of Chemistry.

Fig.17 Schematic electronic structures for TiO2 and TiO2-x(A) and total DOS and partial DOS(Ti) for TiO2 and TiO2-x(B)[27] Copyright from the Royal Society of Chemistry.

Fig.18 Schematic electronic structures for hydrogenated titania(TiO2-xHx) and pristine TiO2(A) and calculated DOS of pristine TiO2 and black TiO2-xHx(B)[26] Copyright from Wiley-VCH.

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