To achieve efficient photocatalytic air purification, we constructed an advanced semimetal-organic Bi spheres-g-C3N4 nanohybrid through the in-situ growth of Bi nanospheres on g-C3N4 nanosheets. This Bi-g-C3N4 compound exhibited an exceptionally high and stable visible-light photocatalytic performance for NO removal due to the surface plasmon resonance (SPR) endowed by Bi metal. The SPR property of Bi could conspicuously enhance the visible-light harvesting and the charge separation. The electromagnetic field distribution of Bi spheres involving SPR effect was simulated and reaches its maximum in close proximity to the Bi particle surface. When the Bi metal content was controlled at 25%, the corresponding Bi-g-C3N4 displayed outstanding photocatalytic capability and transcended those of other visible-light photocatalysts. The Bi-g-C3N4 exhibited a high structural stability under repeated photocatalytic runs. A new visible-light-induced SPR-based photocatalysis mechanism with Bi-g-C3N4 was proposed on the basis of the DMPO-ESR spin-trapping. The photoinduced electrons could transfer from g-C3N4 to the Bi metal, as revealed with time-resolved fluorescence spectra. The function of Bi semimetal as a plasmonic cocatalyst for boosting visible light photocatalysis was similar to that of noble metals, which demonstrated a great potential of utilizing the economically feasible Bi element as a substitute for noble metals for the advancement of photocatalysis efficiency.
Mesoporous C-doped TiO2 nanomaterials with an anatase phase are prepared by a one-pot green synthetic approach using sucrose as a carbon-doping source for the first time. A facile post-thermal treatment is employed to enhance visible light photocatalytic activity of the as-prepared photocatalyst. The enhancement effect of post-thermal treatment between 100 and 300 °C is proved by the photodegradation of gas-phase toluene, and the optimum temperature is 200 °C. Physicochemical properties of the samples are characterized in detail by X-ray diffraction, Raman spectroscopy, N2 adsorption–desorption isotherms, transmission electron microscopy, Fourier transform-infrared spectroscopy, X-ray photoelectron spectroscopy, UV–vis diffuse reflectance spectroscopy, and photoluminescence. The results indicate that the promotive effect of the post-thermal treatment can be attributed to the changes of the catalysts’ surface and optical properties. The results also show that the recombination of electron–hole pairs is effectively inhibited after thermal treatment due to the reduction of surface defects. The facile post-thermal treatment provides a new route for potential industrial applications of C-doped TiO2 nanomaterials prepared by a green approach owing to its low cost and easy scale-up.
Mesoporous C-doped TiO2 nanomaterials with anatase phase are synthesized by a one-step “green” synthetic approach with low-cost inorganic Ti(SO4)2 and glucose as precursors for the first time. This facile method avoids treatment at high temperature, use of expensive or unstable precursors, and production of undesirable byproducts in the synthesis process. The physicochemical properties of as-prepared samples are characterized in detail by X-ray diffraction (XRD), Raman spectroscopy (Raman), N2 adsorption−desorption isotherms, transmission electron microscopy (TEM), Fourier transform-infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TG), UV−vis diffuse reflectance spectroscopy (UV−vis DRS), and photoluminescence (PL). The results indicate that oxygen sites in the TiO2 lattice are substituted by carbon atoms and an O−Ti−C bond is formed. The observed new electronic states above the valence band edge are directly responsible for the electronic origin of the band gap narrowing and visible light photoactivity of the C-doped TiO2. Furthermore, the possible formation mechanism of mesoporous C-doped TiO2 is also discussed. The as-prepared C-doped TiO2 exhibits excellent visible light photocatalytic activity in degradation of toluene in the gas phase compared with that of commercial TiO2 photocatalyst (P25) and C-doped TiO2 prepared by the solid state method. The efficient activity can be attributed to the large surface area and pore volume. Our novel synthesis approach is energy-efficient and environmentally friendly, which can provide an effective approach for industrial applications owing to its low cost and easy scaling up.
Industrial-use catalysts usually encounter severe deactivation after long-term operation for catalytic oxidation of chlorinate volatile organic compounds (CVOCs), which becomes a "bottleneck" for large-scale application of catalytic combustion technology. In this work, typical acidic solid-supported catalysts of MnCeO/HZSM-5 were investigated for the catalytic oxidation of chlorobenzene (CB). The activation energy (E), Brønsted and Lewis acidities, CB adsorption and activation behaviors, long-term stabilities, and surficial accumulation compounds (after aging) were studied using a range of analytical techniques, including XPS, H-TPR, pyridine-IR, DRIFT, and O-TP-Ms. Experimental results revealed that the Brønsted/Lewis (B/L) ratio of MnCeO/HZSM-5 catalysts could be adjusted by ion exchange of H• (in HZSM-5) with Mn (where the exchange with Ce did not distinctly affect the acidity); the long-term aged catalysts could accumulate ca. 14 organic compounds at surface, including highly toxic tetrachloromethane, trichloroethylene, tetrachloroethylene, o-dichlorobenzene, etc.; high humid operational environment could ensure a stable performance for MnCeO/HZSM-5 catalysts; this was due to the effective removal of Cl• and coke accumulations by HO washing, and the distinct increase of Lewis acidity by the interaction of HO with HZSM-5. This work gives an in-depth view into the CB oxidation over acidic solid-supported catalysts and could provide practical guidelines for the rational design of reliable catalysts for industrial applications.
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