Articles (12)

Review

11 July 2024

Photocatalytic Aerobic Conversion of Methane

The direct conversion of methane into high-value chemicals has been a persistent research focus in the fields of chemical engineering and energy. Photocatalysis, as an innovative technology, not only circumvents the issues of catalyst sintering and carbon deposition associated with traditional thermal catalysis but also transcends thermodynamic limitations by providing new reaction pathways. Utilizing molecular oxygen as an oxidant generates various reactive oxygen species, offering unique thermodynamic advantages for methane conversion. This review summarizes the advancements in photocatalytic partial oxidation (PPOM) and oxidative coupling of methane (POCM) using oxygen as an oxidant. It discusses the activation mechanisms and reaction pathways of methane and oxygen in different systems, as well as the application of photochemical cycling strategies in methane conversion. Finally, it addresses the challenges in this field, proposes potential solutions, and offers perspectives on the future development of photocatalytic systems.

Yuxiang Kong
Chunxiang Yang
Yiyu Cai
Xiaowei Mu*
Lu Li*

Article

11 June 2024

Lathyrus aphaca Extract MnO Nanoparticles: Synthesis, Characterization, and Photocatalytic Degradation of Methylene Blue Dye

Our environment has been impacted by man-made pollutants mainly industries make substantial use of synthetic dyes which exhibit cytotoxicity and have significant environmental consequences. Effective photocatalyst-based approaches for degrading synthetic dyes into less toxic chemical are of great interest. Synthesizing nanoparticles (NPs) using biological approaches, particularly plant-based approaches offer advantages, decreasing the risk of NPs losing biocompatibility during synthesis, cost-effectiveness, and eco-friendliness. In this study, we employed a green synthesis method to produce manganese oxide nanoparticles (MnO NPs) utilizing leaf extract from the Lathyrus aphaca plant. The synthesized MnOx NPs were characterized through various techniques; X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), Fourier-transform infrared spectroscopy (FTIR), and UV–visible spectroscopy. XRD analysis showed distinct peaks, indicated the presence crystallographic planes within the MnO2 nanoparticles, thus confirming their crystalline structure. FTIR, showed the presence of the O-O stretching mode at a frequency of 719 cm−1, the presence of MnO6 oxides of manganese, and peak at 548 cm−1 corresponded to the Mn-O stretching mode. Furthermore, the green-synthesized manganese oxide nanoparticles exhibited promising photocatalytic and adsorption capabilities against Methylene Blue (MB) dye, leading to approximately 93% degradation of MB when treated with the green-synthesized MnO nanoparticles derived from plant extract. This highlights the efficacy and potential of these nanoparticles in environmental remediation applications, particularly in the degradation of methylene blue contaminants.

Amir Hassan*
Muhammad Haris
Sana Ullah Khan
Istikhar Khan
Muhammad Akif
Naveed Akhtar

Article

23 April 2024

Visible Light-Driven H2O2 Photoelectrocatalytic Synthesis Over a Tandem Electrode Strategy

Photocatalytic synthesis of hydrogen peroxide (H2O2) can be an environmentally friendly and energy-saving solution. However, the oxygen reduction reaction (ORR) rate is limited due to the low solubility of O2 in water. In this study, a modified BiVO4 (BVO) photoanode combined with an Sn-coordinated phthalocyanine gas diffusion electrode (SnPc-GDE) was employed for the synthesis of H2O2, and the oxy-gen reduction reaction rate was increased through a unique three-phase interface system. When visible light was irradiated on the BVO photoanode, the hole-electron pairs were excited and the oxygen evolution reaction (OER) was driven through the holes, and the excited electrons were transferred to the SnPc-GDE to reduce O2 for the synthesis of H2O2. Oxygen vacancy enrichment on the BVO electrode was achieved by photoetching and annealing under an N2 atmosphere, which effectively improved the carrier separation efficiency. Complexation with a WO3 layer formed a built-in electric field, which further promoted the electron-hole pair separation. The SnPc catalyst-modified GDE electrode has the best selectivity for ORR and remains stable during long-term reactions. Under bias-free conditions, the generation rate of H2O2 reached 952.5 μM·L−1·h−1, with a Faradaic efficiency of 48.4%. This study provided a practical strategy for designing a highly efficient BVO/SnPc-GDE photoelectrochemical system to produce H2O2 based on improvement in electron-hole transmission efficiency and product selectivity.

Chao Chen
Nakata  Takumu
Wenan Cai
Qitao Zhang*
Teruhisa Ohno*

Article

11 April 2024

Exploring Bi4V2O11 as Photoanode for Water Splitting with a Wide Range of Solar Light Capture and Suitable Band Potential

Bi4V2O11 possesses a bandgap of ~1.9 eV, and the band positions of minimum conduction band and maximum valence band straddle the redox potentials of H+/H2 and O2/H2O. In the current work, photoanode made of particulate Bi4V2O11 film displays a wide range of light adsorption. However, when the anode was fabricated by drop-casting and examined for photoelectrochemical water splitting, the photocurrent density of the pristine Bi4V2O11 was low. Improvement has then been carried out by Mo-doping. The Mo-doped Bi4V2O11 photoanode achieves a maximum photocurrent density of 0.3 mA/cm2 after a post deposition necking treatment to improve the connectivity of the drop-cast particles in the film. This material also shows a stability with maintaining 80% photocurrent after 2 h test. Discussion has been made on the displayed performance in PEC water splitting of the Bi4V2O11 materials. Potential solutions have been proposed for this type of promising photoanode material for water splitting.

Xin Zhao
Ningsi Zhang
Yang  Yu
Tao Fang
Jun Hu*
Jianyong Feng*
Zhong Chen*

Article

05 January 2024

Benzene Bridged Carbon Nitride for Efficient Photocatalytic Hydrogen Evolution

Turing the electronic structure by inserting certain functional groups in graphitic carbon nitride (g-C3N4, CN for short) skeleton through molecular doping is an effective way to improve its photocatalytic performance. Herein, we prepare a benzene bridged carbon nitride (BCN) by calcining urea and 1,3,5-tribromobenzene at elevated temperature. The introduction of benzene ring in g-C3N4 layers improves the separation efficiency and lifetime of photogenerated carriers, inhibits the recombination rate of electron/hole pairs, thus the performance of photocatalytic hydrogen evolution improves. The optimal hydrogen evolution rate of 1.5BCN reaches 1800 µmol/h·g, which is nine times that of the pure g-C3N4. DFT calculation proved the benzene bridged CN increased the distance of charge transfer (DCT) and the push-pull electronic effect of intramolecular electrons. This work may provide a pathway for preparing molecular doped g-C3N4 with improved photocatalytic performance.

Junxia Chu
Wencheng Li
Zhijun Cao
Xin Bai
Xi Rao*
Shaohui Zheng*
Yongping Zhang*

Review

12 October 2023

New Trends on Photoswitchable Antibiotics: From Syntheses to Applications

Antibiotics are excreted in the environment after being used to treat bacterial infections in human and animals. These residues are poorly eliminated by the actual wastewater treatment processes, affecting animal, human and environmental health. This has led to the emergence of antibiotic resistance in bacterial pathogens. To combat this problem, photopharmacology has emerged in the last decades. This approach, based on the coupling of a drug with a photochromic component, is a promising way to control antibiotic activity by light irradiation and consequently limit antibioresistance. Thus, this review summarizes the study on the effect of the irradiation light on the antimicrobial activity of coupling compounds.

Amélie Aubert
Antoine Fayeulle
Muriel Vayssade
Muriel Billamboz
Estelle Léonard*

Article

11 October 2023

Fibrous SiC-based Mesoporous Solids for the Photocatalytic Degradation of Organic Pollutants under Artificial Light

SiC-based mesoporous solids with fibrous nanostructure were prepared by impregnation of a polycarbosilane precursor on annealed polyacrylonitrile (PAN) fibers and subsequent pyrolysis. The obtained material exhibits a mesoporous structure and has a specific surface area of ~20 m2/g. It has a semiconducting electronic character with a bandgap of 2.65 eV, i.e., in the visible range. Adsorption tests of methylene blue were performed on the material under dark conditions, which showed an adsorption amount of 78 wt%. The photocatalytic activity of the material was then evaluated for the degradation of the dye under artificial daylight irradiation over a period of 7 h. A degradation of 94 wt% was achieved. Regeneration and reuse of the material was also tested and resulted in 97 wt% degradation after reuse, indicating potential interest of the material as a contactor in environmental remediation devices.

Karla B.Cervantes-Diaz
Julien Cambedouzou*

Article

31 August 2023

Potential Role of Exciton in Photocatalysis

This article commemorates the outstanding Russian scientists E.F. Gross and A.N. Terenin. It revisits their successors’ efforts to develop Terenin’s idea of using excitons, discovered by Gross, for photocatalytic redox reactions on wide-gap semiconductors. Terenin proposed ZnO as the subject of study. To explore the possibility of replacing photogenerated electrons and holes in a redox reaction by an exciton being a quasi-neutral particle, the test reaction of the photoactivated oxygen isotope exchange (POIE) was studied. It was found that many years of initial unsuccessful attempts were due to the fact that the exciton energy is spent on luminescence. In our experiments, the excitons decayed non-radiatively, and the long-lived electron-donor F-type and hole V-type active centers were formed by creating the 2D surface nanostructure ZnO/ZnO1−x/O. These centers allowed to obtain the reaction efficiency 5–8 times higher than with the interband transitions. Thus, the developed 2D surface nanostructure ZnO/ZnO1−x/O resolved the problem of using an exciton in photocatalysis and demonstrated the perspective of this nanostructure as an efficient photocatalyst.

Andrey ALisachenko*
Boris VNovikov

Article

05 July 2023

Photocatalytic Efficiency of Suspended and Immobilized TiO2 P25 for Removing Myclobutanil, Penconazole and Their Commercial Formulations

Fungicide application in viticulture is a major source of surface and groundwater contamination. It is therefore essential to find solutions to stop this environmental pollution. Heterogeneous photocatalysis is an advanced oxidation method for the degradation and mineralization of organic pollutants in water. TiO2 P25 photocatalyst in suspension has been used for removing the fungicides Myclobutanil and Penconazol, and their respective commercial formulations Systhane and Topas, in contaminated water. The apparent kinetic constants kapp of fungicides removal over 30 min batch treatment was higher for a mixture of pure molecules of Myclobutanil and Penconazol than for a mixture of their commercial formulations (17.5 × 10−3 by comparison with 10.3 × 10−3 min−1 for Myclobutanil, and 10.0 × 10−3 by comparison with 2.80 × 10−3 min−1 for Penconazol). TOC removal constants kTOC were similar for the two mixtures, due to the presence of mineral and organic additives in the commercial formulations. To easily recover the photocatalyst after fungicide removal, TiO2 P25 has been supported on β-SiC foam. Fungicides degradation was lower with supported photocatalysts than with the suspension of photocatalyst nanoparticles (NPs) because of a lower concentration of active sites on the supported photocatalyst than in the catalyst suspension. However, catalyst recovery and reuse after fungicide removal is obviously easier with TiO2/β-SiC material than with a suspension of TiO2 which requires long and expensive filtration operations.

Ignace Christian M'Bra
Nicolas Keller
Albert Trokourey
Didier Robert*

Article

03 March 2023

SnS2 Quantum Dots Decorated MoS2 Nanosheets Enabling Efficient Photocatalytic H2 Evolution in CO2 Saturated Water

SnS2/MoS2 heterojunction nanocomposite was prepared by a one-step hydrothermal synthesis method. The nanocomposite exhibited much improved photocatalytic hydrogen evolution performance in CO2 saturated solution compared with pure MoS2 and SnS2 samples. The improved photocatalytic activity was attributed to the S-scheme heterojunction structure between SnS2 quantum dots and MoS2 nanosheets which facilitate electron-hole separation both in MoS2 and SnS2. In the S-scheme structure, the strong reduction ability of SnS2 quantum dots was well maintained for the improved H2 evolution. In situ DRIFT studies allowed us to suggest reaction pathways from CO2 and H2O to photocatalytic H2, CO, and CH4 generation.

Xuelian Chen
Xi Luo
Lei Liu
Jing Ping
Songmei Sun*
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