Acid-activated α-MnO2 for photothermal co-catalytic oxidative degradation of propane: Activity and reaction mechanism.

In order to further reduce the energy consumption of the conventional thermal catalytic oxidation system and improve the degradation efficiency of pollutants, photothermal synergistic catalytic oxidation (PTSCO) system was constructed in this paper with propane as simulated pollutant representing VOCs, and then the modified α-MnO2 catalysts were prepared by using the acid activation method, which were used for the catalytic oxidation of propane in PTSCO. The α-MnO2 with appropriate acid concentration possessed excellent low-temperature reducibility, abundant active oxygen species, fast oxygen migration rate and a large number of acid sites. The optimal catalyst, H0.05-MnO2, had a T90 of 204 °C in the PTSCO system, which reduced by more than 30 °C relative to the α-MnO2 (T90 of 235 °C). Moreover, H0.05-MnO2 demonstrated excellent water resistance and long-term stability (T = 45 h). It was shown that the combination of photocatalysis and thermocatalysis can improve propane degradation by examining the kinetics of propane degradation in the PTSCO system and the conformational relationship of propane degradation by catalysts. Furthermore, a multi-pathway synergistic mechanism between photocatalysis and thermocatalysis in the PTSCO system was proposed. This work provided a theoretical basis for the preparation of high-performance catalysts and the catalytic degradation of propane.

Urea-H2O2 defect engineering of δ-MnO2 for propane photothermal oxidation: Structure-activity relationship and synergetic mechanism determination.

Photothermal catalysis has an advantage in effective and economical elimination technology of volatile organic compounds (VOCs) in the ascendant. Herein, various surface defect engineering routes were adopted to enhance the low-temperature propane oxidation of δ-MnO2. Compared to reducing etchants urea and vitamin C, δ-MnO2 treated with urea - H2O2 exhibited an excellent thermal (T90 = 240 ℃) and photothermal (T90 = 196 ℃) activities of propane oxidation. Urea - H2O2 treatment provided high concentration of Mn4+ and surface-active oxygen (Mn4+-Osur) species as surface-active sites, and produced numerous oxygen vacancies to improve charge separation and superoxide species generation capacity. Thus, the photothermal conversion efficiency and low-temperature reducibility were remarkably enhanced. Furthermore, the photothermal synergistic catalytic mechanism was proposed based on in-situ diffuse reflectance infrared Fourier transform spectroscopy and control experiments. The strategy here offered insight into the rational design of efficient transition catalysts, and in-depth understanding of the photothermal catalytic VOCs removal mechanism.

Adsorption coupling photocatalytic removal of gaseous n-hexane by phosphorus-doped g-C3N4/TiO2/Zn(OAc)2-ACF composites.

VOCs emission reduction in the petroleum and petrochemical industry is a hot and difficult topic at present. The single method may not be able to meet the actual treatment status. Therefore, the adsorption coupled photocatalytic degradation technology was used to remove VOCs. Phosphorus-doped carbon nitride (PCN) and PCN/TiO2 were prepared by hydrothermal synthesis and sol-gel method, and then PCN/TiO2/Zn(OAc)2-ACF composites were prepared by ultrasonic impregnation on zinc acetate modified activated carbon fibers (Zn(OAc)2-ACF). The removal efficiency of n-hexane by composite materials was explored in a self-made reactor, and the factors affecting removal efficiency, removal mechanism, and possible ways of degradation were investigated. The results showed that under the optimum reaction conditions (initial concentration of n-hexane 200 mg/m3, space velocity 1000 h-1, light intensity 24 W, mass fraction of doped PCN 6%, loading twice, calcination temperature 450 °C), PCN/TiO2/Zn(OAc)2-ACF composite has the highest removal efficiency of n-hexane (90.2%). The adsorption capacity of the composites after doping the P element was 215.3 mg/g, which did not enhance the adsorption performance compared with that before doping, but the removal rate of n-hexane was higher. This showed that doping P element was helpful to enhance the photocatalytic activity of the composites.

Synergistic effect of adsorption and photocatalysis for the degradation of toluene by TiO2 loaded on ACF modified by Zn(CH3COO)2.

Activated carbon fiber (ACF) was modified by Zn(NO3)2, ZnCl2, and Zn(CH3COO)2), respectively, and then, TiO2 was loaded on the modified ACFs. The adsorption and photocatalysis performance were explored through the removal of toluene, and TiO2/ACF-Ac modified by Zn(CH3COO)2) with the best toluene degradation performance was selected. The characterization results of a scanning electron microscope (SEM), X-ray diffraction spectra (XRD), and Fourier transform infrared spectrometer (FTIR) indicated that the samples were rough, and TiO2 was mainly loaded on the surface containing large amount of oxygen-containing functional groups in anatase phase. An ultraviolet-visible diffuse reflectance spectrophotometer (UV-vis DRS) revealed that the catalyst enhanced the light response range. The photoelectric chemical experiment results demonstrated that the modified ACFs remarkably improved the charge transmission and the separation efficiency of electrons and holes. The adsorption saturation time reached 40 h and toluene photodegradation rate was 70%. Four toluene degradation intermediate products were determined by GC-MS, and the removal mechanism of toluene by TiO2/ACF-Ac was discussed.