Multiple contaminants including heavy metals and phenolic compounds are normally co-exist in wastewater, which caused the treatment process is rather complicated. Herein, the synergistic photoredox of Cr(VI) and p-cresol (pC) by innovative fibrous silica zirconia (FSZr) photocatalyst was reported. The high surface area of FSZr comprised of microspheres with a bicontinuous concentric lamella structure morphology consisted of silica, while its core consisted of ZrO2 structure. The rearrangement of FSZr framework increased the crystallinity, formed Si-O-Zr bonds and narrowed the band gap of ZrO2 for enhanced of photoredox of Cr(VI) and pC. Compared to the reaction, the photoredox efficiency of FSZr for removing Cr(VI) and pC in simultaneous system was found to be 96 % and 59 %, respectively which are higher than that in its single system owing to the efficient electron-hole charge separation. Phenolic compound with high degree of electron donating group gave beneficial effect to photoreduction of Cr(VI). Consequently, a proposed mechanism involving multi-photoredox pathway were proposed based on photoredox reaction and scavengers studies. FSZr sustained the simultaneous photoredox activities after five runs demonstrating its possibility to be use in the wastewater treatment of various pollutants.
The co-existence of heavy metals and organic compounds including Cr(VI) and p-cresol (pC) in water environment becoming a challenge in the treatment processes. Herein, the synchronous photocatalytic reduction of Cr(VI) and oxidation of pC by silver oxide decorated on fibrous silica zirconia (AgO/FSZr) was reported. In this study, the catalysts were successfully developed using microemulsion and electrochemical techniques with various AgO loading (1, 5 and 10 wt%) and presented as 1, 5 and 10-AgO/FSZr. Catalytic activity was tested towards simultaneous photoredox of hexavalent chromium and p-cresol (Cr(VI)/pC) and was ranked as followed: 5-AgO/FSZr (96/78%) > 10-AgO/FSZr (87/61%) > 1-AgO/FSZr (47/24%) > FSZr (34/20%). The highest photocatalytic activity of 5-AgO/FSZr was established due to the strong interaction between FSZr and AgO and the lowest band gap energy, which resulted in less electron-hole recombination and further enhanced the photoredox activity. Cr(VI) ions act as a bridge between the positive charge of catalyst and cationic pC in pH 1 solution which can improve the photocatalytic reduction and oxidation of Cr(VI) and pC, respectively. The scavenger experiments further confirmed that the photogenerated electrons (e-) act as the main species for Cr(VI) to be reduced to Cr(III) while holes (h+) and hydroxyl radicals are domain for photooxidation of pC. The 5-AgO/FSZr was stable after 5 cycles of reaction, suggesting its potential for removal of Cr(VI) and pC simultaneously in the chemical industries.
Nanostructured photocatalysts commonly offered opportunities to solve issues scrutinized with the environmental challenges caused by steep population growth and rapid urbanization. This photocatalyst is a controllable characteristic, which can provide humans with a clean and sustainable ecosystem. Over the last decades, one of the current thriving research focuses on visible-light-driven CeO2-based photocatalysts due to their superior characteristics, including unique fluorite-type structure, rigid framework, and facile reducing oxidizing properties of cerium's tetravalent (Ce4+) and trivalent (Ce3+) valence states. Notwithstanding, owing to its inherent wide energy gap, the solar energy utilization efficiency is low, which limits its application in wastewater treatment. Numerous modifications of CeO2 have been employed to enhance photodegradation performances, such as metals and non-metals doping, adding support materials, and coupling with another semiconductor. Besides, all these doping will form a different heterojunction and show a different way of electron-hole migration. Compared to conventional heterojunction, advanced heterojunction types such as p-n heterojunction, Z-scheme, Schottky junction, and surface plasmon resonance effect exhibit superior performance for degradation owing to their excellent charge carrier separation, and the reaction occurs at a relatively higher redox potential. This review attends to providing deep insights on heterojunction mechanisms and the latest progress on photodegradation of various contaminants in wastewater using CeO2-based photocatalysts. Hence, making the CeO2 photocatalyst more foresee and promising to further development and research.
With the tremendous development of the economy and industry, the pollution of water is becoming more serious due to the excessive chemical wastes that need to remove thru reduction or oxidation reactions. Simultaneous removal of dual pollutants via photocatalytic redox reaction has been tremendously explored in the last five years due to effective decontamination of pollutants compared to a single pollutants system. In a photocatalysis mechanism, the holes in the valence band can remarkably promote the oxidation of a pollutant. At the same time, photoexcited electrons are also consumed for the reduction reaction. The synergistic between the reduction and oxidation inhibits the recombination of electron-hole pairs extending their lifetime. In this review, the binary pollutants that selectively removed via photocatalysis reduction or oxidation are classified according to heavy metal-organic pollutant (HM/OP), heavy metal-heavy metal (HM/HM) and organic-organic pollutants (OP/OP). The intrinsic between the pollutants was explained in three different mechanisms including inhibition of electron-hole recombination, ligand to metal charge transfer and electrostatic attraction. Several strategies for the enhancement of this treatment method which are designation of catalysts, pH of mixed pollutants and addition of additive were discussed. This review offers a recent perspective on the development of photocatalysis system for industrial applications.
Fibrous silica-titania (FST) catalysts were synthesized by microemulsion followed by silica seed-crystal crystallization methods under various molar ratios of toluene to water (T/W). The catalysts were characterized by XRD, UV-DRS, FESEM, TEM, AFM, N2 adsorption-desorption, FTIR, and ESR. The results revealed that altering the T/W ratio affected the growth of the silica and titania and led to different size, fiber density, silica-titania structure, and number of hydroxyl groups, as well as oxygen vacancies in the FSTs, which altered their behavior toward subsequent application. Photodegradation of ibuprofen (IBP) are in the following order: FST(6:1) (90%) > FST(5:1) (84%) > FST(7:1) (79%) > commercial TiO2 (67%). A kinetics study using Langmuir-Hinshelwood model illustrated that the photodegradation followed the pseudo-first-order and adsorption was the rate-limiting step. Optimization by response surface methodology (RSM) showed that the pH, initial concentration, and catalyst dosage were the remarkable parameters in photodegradation of IBP. The FST (6:1) maintained its photocatalytic activities for up to five cycles reaction without serious catalyst deactivation, and was also able to degrade other endocrine-disrupting chemicals, indicating its potential use for the treatment of those chemicals in wastewater.
Ternary CuO/AgO/FSZr photocatalysts were fabricated via the hydrothermal and electrochemical methods with three different CuO loading (1, 3 and 5 wt%), indicated as 1CuO/AgO/FSZr, 3CuO/AgO/FSZr and 5CuO/AgO/FSZr. The photocatalytic reaction was tested towards simultaneous chromium (VI) photoreduction and p-cresol photooxidation and the performance in order as follow: 3CuO/AgO/FSZr > 5CuO/AgO/FSZr > 1CuO/AgO/FSZr > AgO/FSZr > FSZr. CuO/AgO/FSZr photocatalysts showed an improvement in photocatalytic activity compared to AgO/FSZr and FSZr due to the reduction potential of chromium (VI) aligned closer to the conduction band of CuO and provided abundant free active electrons (e-) and holes (h+) with efficient transportation and migration. Interestingly, the 3CuO/AgO/FSZr was established as the best photocatalyst with 98% reduction of chromium (VI) and 83% oxidation of p-cresol simultaneously, owing to its strong corporation between the metal oxides and support and higher total pore volume. The Langmuir-Hinshelwood model were employed for kinetics which followed the pseudo-first-order kinetics model well. Based on the simultaneous photocatalytic mechanism, chromium (VI) and p-cresol were directly reduced and oxidized by e- and h+, respectively. The response surface methodology (RSM) discovered that the quadratic term initial concentration of chromium (VI) is the main significant factor in photocatalytic performance. The optimum parameters for simultaneous photoredox of chromium (VI) and p-cresol predicted from RSM are 9.6 mg L-1 of chromium (VI) concentration, 9.8 mg L-1 of p-cresol concentration and 0.32 g L-1 of catalyst dosage. Under these conditions the error between the predicted and experimental values is only 3.7%. The 3CuO/AgO/FSZr sustained the photocatalytic performance after reused for five cycles and could oxidized various organic pollutants as well as reduced chromium (VI) simultaneously.