Strategies to Enhance ZnO Photocatalyst's Performance for Water Treatment: A Comprehensive Review.

Despite the photocatalytic organic pollutant degradation using ZnO started in 1910-1911, many challenges are still ahead, and several critical issues have to be addressed. Large band gap, and short life-time of photogenerated electrons and holes are critical issues negatively affect the photocatalytic activity of ZnO. Various approaches have been introduced to overcome these issues including intrinsic doping, extrinsic doping, and heterostructure. This review introduces unique and deep insights into tuning of the photocatalytic activity of ZnO. It starts by description of how to tune the photocatalytic activity of pristine ZnO through tuning its morphology, surface area, exposed face, and intrinsic defects. Afterward, the review explains how the Z-scheme approach succeed to address the redox weakened issue of heterojunction approach. In general, this review provides a clear image that helps the researcher to tune the photocatalytic activity of pristine ZnO and its heterostructure.

Fabrication of rGO-bridged TiO2/g-C3N4 Z-scheme Nanocomposites via Pulsed Laser Ablation for Efficient Photocatalytic CO2 Reduction.

Highly efficient photocatalysts can be fabricated using favorable charge transfer nanocomposite channel structures. This study adopted pulsed laser ablation in liquid (PLAL) to obtain rGO-bridged TiO2/g-C3N4 (rGO-TiO2/g-C3N4) photocatalytic Z-scheme without the need for noble metals. In addition to evaluating the resulting nanocomposite's (comprising rGO nanosheets, TiO2 nanotubes, and g-C3N4 nanosheets) CO2 reduction effectiveness, its chemical, morphological, structural, and optical characteristics were examined using various analytical techniques. The findings revealed a synergistic interaction between g-C3N4 and TiO2, suggesting the presence of unique interfacial bonding, as well as enhanced visible light absorption. Notably, the ternary rGO-TiO2/g-C3N4 Z-scheme exhibits an excellent photocatalytic performance by photocatalytically converting CO2 into CO and CH4, with 81% selectivity towards the CO and 1.91% apparent quantum efficiency at 420 nm. Thus, the findings can pave the way for various Z-scheme systems in wide photocatalytic applications.

2D/1D MoS2 /TiO2 Heterostructure Photocatalyst with a Switchable CO2 Reduction Product.

Regulating the transfer pathway of charge carriers in heterostructure photocatalysts is of great importance for selective CO2 photoreduction. Herein, the charge transfer pathway and in turn the redox potential succeeded to regulate in 2D MoS2 /1D TiO2 heterostructure by varying the light wavelength range. Several in situ measurements and experiments confirm that charge transfer follows either an S-scheme mechanism under simulated solar irradiation or a heterojunction approach under visible light illumination, elucidating the switchable property of the MoS2 /TiO2 heterostructure. Replacing the simulated sunlight irradiation with the visible light illumination switches the photocatalytic CO2 reduction product from CO to CH4. 13 CO2 isotope labeling confirms that CO2 is the source of carbon for CH4 and CO products. The photoelectrochemical H2 generation further supports the switching property of MoS2 /TiO2 . Unlike previous studies, density functional theory calculations are used to investigate the band structure of Van der Waals MoS2 /TiO2 S scheme after contact, allowing to propose accurate charge transfer pathways, in which the theoretical results are well matched with the experimental results. This work opens the opportunity to develop photocatalysts with switchable charge transport and tunable redox potential for selective artificial photosynthesis.

Sulfate radicals induced from peroxymonosulfate on electrochemically synthesized TiO2-MoO3 heterostructure with Ti-O-Mo bond charge transfer pathway for potential organic pollutant removal under solar light irradiation.

Here, a novel method for synthesis of heterostructured TiO2-MoO3 (MT) nanosheets photocatalyst by utilizing a facile electrochemical method and examined it's photocatalytic activity by the degradation of tetracycline hydrochloride (TCH), a model of organic pollutants, in the presence of peroxymonosulfate (PMS) under solar light irradiation (SL) was reported for the first time. The influence of several factors on the degradation efficiency including the initial concentration of TCH, solution pH, catalyst dosage, PMS concentration, and the existence of inorganic anions was explored. The MT-15/PMS system displayed a promising photocatalytic performance and up to 97% of TCH was degraded in 90 min the rate of the degradation reaction of MT-15/PMS was the highest (0.05299 min-1) compared to 0.00251, 0.00337, 0.00546, 0.00735, 0.01337min-1of TiO2-P25, TiO2-P25/PMS, MoO3, MoO3/PMS, and MT-15 respectively. The enhancement can be attributed to several reasons. First, the 2D morphology of the optimized heterostructure photocatalyst plays a significant role in providing much more active sites on its surface. Next, the boosted light absorption efficiency and higher photoproduced electron-hole pair separation ability, induced by the unique direct transformation of photogenerated electrons from the valance band of TiO2 to the conduction band of MoO3 via the Ti-O-Mo bond formed at the interface of MT heterostructure. Finally, the appropriate accessible reactive sites for the activation of PMS together with the synergistic effect between activation of PMS and photocatalytic processes eased the production of active species for the degradation of pollutants. Based on the scavenger experiments and EPR analysis, hydroxide and sulfate radicals were found to be the dominant free radical active species in the degradation process. Furthermore, the synergistic degradation reaction mechanism was proposed.

One-Step Hydrothermal Synthesis of Anatase TiO2 Nanotubes for Efficient Photocatalytic CO2 Reduction.

The hydrothermal dissolution-recrystallization process is a key step in the crystal structure of titania-based nanotubes and their composition. This work systematically studies the hydrothermal conditions for directly synthesizing anatase TiO2 nanotubes (ATNTs), which have not been deeply discussed elsewhere. It has been well-known that ATNTs can be synthesized by the calcination of titanate nanotubes. Herein, we found the ATNTs can be directly synthesized by optimizing the reaction temperature and time rather than calcination of titanate nanotubes, where at each temperature, there is a range of reaction times in which ATNTs can be prepared. The effect of NaOH/TiO2 ratio and starting materials was explored, and it was found that ATNTs can be prepared only if the precursor is anatase TiO2, using rutile TiO2 leads to forming titanate nanotubes. As a result, ATNTs produced directly without calcination have excellent photocatalytic CO2 reduction than titanate nanotubes and ATNTs prepared by titanate calcination.