Photocatalytic System Research Articles

Plasmonic antenna enhancement on Pd cluster towards high selective FDCA production

2,5-Furandicarboxylic acid (FDCA), an excellent precursor for producing value-added green polymers, has recently garnered much attention. Traditional methods for oxidizing 5-Hydroxymethylfurfural (HMF) to FDCA typically require harsh conditions, such as high pressure, high temperature, and non-eco-friendly reactants, making them neither green nor economical. In this study, we present a novel photocatalytic system utilizing a plasmonic antenna effect to enhance Pd clusters supported on ceria (CeO2). This system drives the transformation from HMF to FDCA under ambient conditions, achieving an impressive yield of over 90% within 4 h under green light irradiation. Notably, the palladium content in this system is minimal. This discovery could pave the way for the development of new photocatalytic systems with varied nanostructures or elemental compositions for efficient chemical reactions.

A Rootless Duckweed-Inspired Flexible Artificial Leaf from Plasmonic Photocatalysts.

The naturally existing leaves are ubiquitous two-dimensional flexible solar-to-chemical conversion systems that can run continuously in a sustainable manner. However, the current artificial photocatalytic systems are unable to achieve this due to the grand challenge in integrating existing photocatalysts in a flexible layout with high conversion efficiency and the ability to function independently. Here, we report on a rootless duckweed-inspired artificial leaf based on a lightweight, flexible, Janus plasmonic nanosheet-integrated sponge. The Janus plasmonic catalytically active nanosheet was made from self-assembled gold nanocube nanoassemblies grown on the porous sponges, which were further coated with an ultrathin palladium layer on one side via a ligand symmetry-breaking method. This sponge-based photocatalytic system is lightweight yet able to float on a water surface and conducts the gas-liquid reaction without auxiliary pumping and mixing devices. In a model reaction of 4-nitrophenol reduction, this floating leaf could achieve 2.5-fold and 65-fold higher efficiency than the corresponding dispersion and precipitation systems, respectively. The film theory is used to explain the sponge-based lightweight solar-to-chemical conversion system in a detailed kinetic and thermodynamic analysis, including the reaction rate constant, activation energy, enthalpy, entropy, Gibbs energy, and equilibrium constant.

Strong Built-In Electric Field-Assisted ZnO/ZnIn2S4 S-Scheme Heterostructure to Promote Photocatalytic Hydrogen Production.

Photocatalysis is an eco-friendly and significant perspective for generating hydrogen. Our study investigated the ZnO/ZnIn2S4 heterojunction photocatalytic system prepared through hydrothermal technique. Accordingly, the ZnIn2S4 nanofibers loaded with 11 mol % ZnO exhibited the hydrogen evolution rate of about 1998 μmol g-1 h-1, which was 2.6 times higher than the pristine ZnIn2S4. In situ electron paramagnetic resonance results proved the S-scheme photocarrier transport route, and in situ KPFM further characterized the internal electric field between ZnO and ZnIn2S4. The development of S-scheme heterojunctions allows for the spatial segregation and transport of charges by preserving photoexcited holes and electrons with a tremendous redox potential. Furthermore, the photoelectrochemical analysis demonstrated that the S-scheme heterojunction could also be employed for the separation of photoexcited species.

High-efficiency and stable Z-scheme heterojunction of Co9S8 anchored by g-C3N4 for peroxymonosulfate activation

Photocatalytic technology and peroxymonosulfate (PMS) based advanced oxidation technology have been proven to be simple and effective strategies for recalcitrant organic pollutants degradation. In this work, we designed and prepared a coupled photocatalytic and advanced oxidation system for sulfamethazine (SMR) antibiotics degradation. Firstly, a series of Z-scheme Co9S8/g-C3N4 heterojunction photocatalysts are prepared by a simple two-step method and further work as PMS activators. The prepared Co9S8/g-C3N4 photocatalysts exhibit a great improvement in electron-hole pairs migration and visible-light response due to heterojunction formation. In addition, the g-C3N4 acts as a substrate to anchor the Co9S8 nanoparticle, which suppresses the Co9S8 leaching and prevents the Co9S8 oxidation. Consequently, the Co9S8/g-C3N4/PMS system displayed an improved SMR degradation ability (93 % for Co9S8/g-C3N4/PMS vs. 86 % for Co9S8/g-C3N4). After the fourth cyclic degradation experiment, the Co9S8/g-C3N4/PMS system still maintained a comparatively high degradation rate. Considering its good properties and better degradation performance, we propose that the synergistic effect of photocatalytic technology and PMS possess a promising prospect for application in environmental treatment.

Tetraphenylethene-Based Molecular Cage with Coenzyme FAD: Conformationally Isomeric Complexation toward Photocatalysis-Assisted Photodynamic Therapy.

Flavin adenine dinucleotide (FAD), serving as a light-absorbing coenzyme factor, can undergo conformationally isomeric complexation within different enzymes to form various enzyme-coenzyme complexes, which exhibit photocatalytic functions that play a crucial role in physiological processes. Constructing an artificial photofunctional system using FAD or its derivatives can not only develop biocompatible photocatalytic systems with excellent activities but also further enhance our understanding of the role of FAD in biological systems. Here, we demonstrate a supramolecular approach for constructing an artificial enzyme-coenzyme-type host-guest complex with photoinduced catalytic function in water. First, we have designed and synthesized a water-soluble tetraphenylethene (TPE)-based octacationic molecular cage (1) with a large and flexible cavity, which can adaptively encapsulate with two FAD molecules with "U-shaped" conformation (uFAD) to form a 1:2 host-guest complex (1⊃uFAD2) in water. Second, based on the conformationally isomeric complexation of FAD within 1, the 1⊃uFAD2 complex facilitates electron and energy transfers to molecular oxygen upon the white-light illumination, efficiently producing reactive oxygen species (ROS) such as superoxide radical (O2•-) and singlet oxygen (1O2). To our knowledge, the 1⊃uFAD2 complex acts as a photocatalyst to achieve the highest turnover frequency (TOF) of 35.6 min-1 for the photocatalytic oxidation reaction of NADH via a photoinduced superoxide radical catalysis mechanism in an aqueous medium. At last, combining the cytotoxic effects of ROS and the disruption of the intracellular redox balance involving NADH, 1⊃uFAD2 as a supramolecular photosensitizer displays an excellent oxygen-independent photocatalysis-assisted photodynamic therapy in hypoxic tumors.

Rationally designed photothermal-pyroelectric Fe0.9Ni0.1S2/ZnSnO3 Z-scheme heterojunction for promoting electrical charge polarization towards optimized photocatalytic H2 evolution and intermolecular N-N coupling reaction

Developing a photocatalytic composite system that can couple hydrogen (H2) evolution and benzylamine (BA) oxidation is a challenging task, especially while avoiding sacrificial agents and value-added chemicals. Here, a practical approach is reported to develop a photothermal-pyroelectric-Fe0.9Ni0.1S2/ZnSnO3 photocatalytic system with core–shell and Z-scheme heterostructure via hydrothermal and annealing methods. Although Fe0.9Ni0.1S2 nanoparticles (NPs) could convert most of near-infrared (NIR) light energy into heat energy to drive the pyroelectric effect of ZnSnO3, it also results in temperature fluctuations (ΔT) in the system, causing natural polarization and thermoelectric effects under the condensed water circulation. As a result, the as-designed Fe0.9Ni0.1S2/ZnSnO3-2 composites could yield up to 7.194 mmol g-1h−1 with exceptional photocatalytic H2 evolution under simulated sunlight. This result is 5.41 and 4.92-fold those of Fe0.9Ni0.1S2 and ZnSnO3, respectively, with 16.66 % apparent quantum yield (AQY) under 365 nm monochromatic light. At the same time, the composites could also oxidize BA and yield up to 6.640 mmol g-1h-1n-benzylidene benzylamine (NBBA) with a 90.2 % selectivity. Due to the synergistic effect of Z-scheme’s built-in electric field and photothermal-pyroelectric of Fe0.9Ni0.1S2/ZnSnO3, the surface charges released on them could direct the charge transfer pathways and restrain their recombination with accelerated electron transfer kinetics, thus extending the carrier lifetime. This work offers a new perspective for designing electrical charge polarized by the photothermal-pyroelectric effect, which can enhance H2 evolution and BA oxidation concurrently.

Fabrication of pyridine incorporated and O-doped g-C3N4/COF: A type-II heterojunction for enhanced hydrogen production under visible light irradiation

The fabrication of heterojunction photocatalysts is important for achieving highly efficient electron transfer, charge separation, and catalytic activity. In this study, we report the successful creation of a type II heterojunction between pyridine incorporated and O-doped g-C3N4 (POCN) and a covalent organic framework (COF). The heterojunction formation significantly reduced the fluorescence intensity of the POCN/COF, indicating effective separation of electron-hole pairs. Additionally, POCN/COF demonstrated excellent interface charge transfer resistance and photocurrent response. Its hydrogen production rate was remarkably high at 3500 μmol g⁻1 h⁻1, about 1.6 times that of pure COF (2200 μmol g⁻1 h⁻1) and 3.5 times that of the physical mixture (1000 μmol g⁻1 h⁻1), and it also exhibited enhanced stability. This indicates that it can be effectively fabricated into a heterojunction of POCN and COF. The optimal value for adding POCN was approximately 5 wt% of COF. This demonstrates greater activity compared to other composite catalysts made from graphitic carbon nitride and COF. This study presents a valuable approach for fabricating reusable heterojunction photocatalytic systems and efficiently generating hydrogen from natural energy sources.

Highly efficient Zn(O,S)/Mo(O,S)2 oxysulfide heterostructure photocatalyst for organic pollutant degradation

Environment and energy are presently some of the highest priority topics for mankind that need to be addressed. Organic pollutants are toxic and carcinogenic for human and aquatic life hence their presence in water even in low concentrations can cause serious health problems. Photodegradation of organic pollutants by utilizing oxide-based heterostructure photocatalysts is the promising approach to carry out remediation efficiently ascribed to the advanced optoelectronic and structural superiority of oxide photocatalysts. The Zn(O,S)/Mo(O,S)2 composites were synthesized via a facile solvothermal method at low temperatures. Several methods were used to characterize the composite morphology, structure, electrical conductivity, chemical composition, and optical characteristics. The heterostructured Zn(O,S)/Mo(O,S)2 oxysulfide was employed successfully in the photocatalytic degradation of organic pollutants. Among the as-prepared samples, the 30-ZnMoOS composite catalyst was found to have the highest photodegradation performance on various organic dye pollutants. The photocatalytic activity of the as-synthesized Zn(O,S)/Mo(O,S)2 samples was assessed on the photodegradation of different kinds of organic dyes under visible light irradiation. The photocatalytic degradation efficiency of 30-ZnMoOS composite over 10 ppm neutral red (NR), methylene blue (MB), rhodamine B (Rh B), and methyl orange (MO) was found to be 99.6 %, 99.9 %, 99.5 %, and 98.8 % within 40, 45, 180, and 180 min, respectively, under visible light illumination. In the present photocatalytic system, the superoxide (.O2-) anions, hydroxyl (.OH) radicals, and holes (h+) are proposed to be the direct reactive species causing the photodegradation of organic dyes.

Hydroxyl Radical Mediated Heterogeneous Photocatalytic Baeyer-Villiger Oxidation over Covalent Triazine/Heptazine-Based Frameworks.

The Baeyer-Villiger oxidation of ketones to the corresponding lactones/esters is a classic and essential reaction in the chemical industry. However, this oxidation process has not yet been achieved in ambient conditions with the aid of oxygen and heterogeneous photocatalysts. In this study, we developed an organic photocatalytic system using covalent triazine/heptazine-based frameworks (CTF-TB/CHF-TB) to enable the B-V oxidation reaction under mild conditions through a cascade reaction pathway. Experimental data and theoretical calculations showed that heptazine/triazine units can "chelate" and decompose the in situ generated H2O2 into hydroxyl radicals (•OH). Compared to conventional methods that primarily involve metal-activated benzaldehyde at elevated temperatures (e.g., 60 oC), the •OH generated in our study can readily cleave the C-H bond of benzaldehyde, forming an active intermediate that drives subsequent sequential processes: O2→H2O2→•OH→Ph-CO•→Ph-COOO•. By employing this photocatalytic process, a yield of 91% and a selectivity of over 99 % were obtained in the oxidation of cyclohexanone to caprolactone at room temperature. This performance is comparable to the state-of-the-art catalysts, and our CHF-TB catalyst demonstrates impressive reusability, maintaining a high yield after 5 consecutive runs. This work presents a straightforward approach for C-H cleavage by organocatalysts to produce ε-caprolactone in a mild manner by Baeyer-Villiger oxidation.

Prussian Blue Analogues-Derived ZnFe2O4 in CuO/ZnFe2O4 p-n Junction for H2 Production.

ZnFe2O4 is an n-type semiconductor spinel oxide with promising applications in various fields, including photocatalysis. This study reports the successful synthesis of a novel ZnFe2O4 derivative based on Prussian Blue Analogues (PBAs) through an electrosynthesis method. To enhance photocatalytic performance, the synthesized ZnFe2O4 was employed as a cocatalyst in p-n junction materials, specifically CuO/ZnFe2O4. Our findings reveal that introducing ZnFe2O4 could significantly improve the photocatalytic activity and hydrogen (H2) production rate of the CuO/ZnFe2O4 system compared to bare CuO. This enhancement was sustained over an extended operational period, indicating the material's potential for long-term use in photocatalytic applications. The superior performance of the ZnFe2O4 cocatalyst is attributed to its efficient charge separation and improved light absorption properties, which collectively contribute to higher photocatalytic efficiency. This study highlights the potential of PBA-based derivative ZnFe2O4 as an effective cocatalyst in developing advanced photocatalytic systems for sustainable hydrogen production.

Integration of polyoxometalate into defective UiO-66-NH2(Zr/Hf) for visible-light-driven hydrogen photogeneration

UiO-66 plays a crucial role in photocatalytic systems due to its superior stability and tunability. However, the charge transfer from organic ligands to metals is rarely involved in the photo-excitation of the pristine material. Herein, several Keggin-type Cs2.5H0.5PW12O40 (CsPW) were successfully incorporated into a bimetallic metal-organic framework (MOF) using a one-pot, one-step method, resulting in a series of defective CsPW@UNH(Hf-Zr) as optimized photocatalysts for visible-light-driven hydrogen evolution. Further investigations demonstrate that a Z heterojunction mechanism proceeds in the CsPW@UNH(0.65Hf) heterojunction to boost the charge separation via the chemical interaction between the CsPW and UNH(0.65Hf) components. The hydrogen evolution rate for 5 %CsPW@UNH(0.65Hf) is nearly two orders of magnitude greater than that of the bare UNH(Zr). The coexistence of Hf3+ and Zr3+ was observed in defective polyoxometalate-encapsulated MOF (POM@MOF) for the first time during photocatalysis, confirming the successful conjugated π electrons transition from the amine-containing ligand to bimetallic cluster. This study offers a novel guideline for exploring efficient MOF-based photocatalysts through defect engineering.

Metal Cocatalyst Engineering in Metal-Semiconductor Hybrid Photocatalysts Achieves a Fivefold Enhancement of Hydrogen Evolution.

This study explores the optimal morphology of photochemical hydrogen evolution catalysts in a one-dimensional system. Systematic engineering of metal tips on precisely defined CdSe@CdS dot-in-rods is conducted to exert control over morphology, composition, and both factors. The outcome yields an optimized configuration, a Au-Pt core-shell structure with a rough Pt surface (Au@r-Pt), which exhibits a remarkable fivefold increase in quantum efficiency, reaching 86 % at 455 nm and superior hydrogen evolution rates under visible and AM1.5 G irradiation conditions with prolonged stability. Kinetic investigations using photoelectrochemical and time-resolved measurements demonstrate a greater extent and extended lifetime of the charge-separated state on the tips as well as rapid water reduction kinetics on high-energy surfaces. This approach sheds light on the critical role of cocatalysts in hybrid photocatalytic systems for achieving high performance.

Z-Scheme Ag2S-Ag-In2O3 Heterostructure with Efficient Antibiotics Removal under Natural Sunlight.

The widespread distribution of antibiotics in natural waters is a great threat to human health. Photocatalytic degradation is an environmentally friendly technology to remediate antibiotic-polluted waters, driven by endless solar energy. Herein, a Z-scheme Ag2S-Ag-In2O3 heterostructure photocatalyst is prepared to remove antibiotics under environmental conditions. Under natural sunlight (light intensity: ∼78 mW/cm2) irradiation, the optimal Ag2S-Ag-In2O3 (10-ASAIO) exhibits considerable performance for decomposing diverse antibiotics, including norfloxacin (NOR), tetracycline hydrochloride, sulfisoxazole, ciprofloxacin, chlortetracycline hydrochloride, and ofloxacin. The NOR photodegradation rate constant of 10-ASAIO reaches 0.025 min-1, which is 12.50, 5.00, and 6.25 times higher than that of In2O3 (0.002 min-1), Ag-In2O3 (0.005 min-1), and Ag2S-In2O3 (0.004 min-1), respectively. This performance of the 10-ASAIO photocatalyst for decomposing NOR under natural sunlight exceeds most of the previously reported photocatalysts under a xenon lamp. Particularly, due to the intermittency of natural sunlight, a light-emitting diode (LED) lamp (light intensity: 5.1 mW/cm2) is also used as a light source, and 72.20% of NOR can be degraded with irradiation for 12 h. The effects of many water characteristics (water bodies, coexisting inorganic anions, pH, and humic acid) on the degradation performance of 10-ASAIO have been investigated, which exhibits stable degradation efficiency in variable aquatic environments. A 10-ASAIO catalyst-coated frosted glass sheet is fabricated to settle the problem of recovery of powder photocatalysts, and the immobilized catalyst shows outstanding activity and stability to decompose NOR. The photocatalytic mechanism and pathway of degrading NOR over 10-ASAIO have also been systemically investigated and proposed. The ecotoxicity (phytotoxicity and biotoxicity) of the 10-ASAIO photocatalyst and treated NOR solution have been tested by their toxic effects on cabbage seeds and Staphylococcus aureus (S. aureus). This work provides a feasible photocatalytic system for environmental pollutant remediation under natural sunlight or an LED lamp.

Efficient Removal of PFASs Using Photocatalysis, Membrane Separation and Photocatalytic Membrane Reactors.

Perfluoroalkyl and polyfluoroalkyl substances (PFASs) are persistent compounds characterized by stable C-F bonds giving them high thermal and chemical stability. Numerous studies have highlighted the presence of PFASs in the environment, surface waters and animals and humans. Exposure to these chemicals has been found to cause various health effects and has necessitated the need to develop methods to remove them from the environment. To date, the use of photocatalytic degradation and membrane separation to remove PFASs from water has been widely studied; however, these methods have drawbacks hindering them from being applied at full scale, including the recovery of the photocatalyst, uneven light distribution and membrane fouling. Therefore, to overcome some of these challenges, there has been research involving the coupling of photocatalysis and membrane separation to form photocatalytic membrane reactors which facilitate in the recovery of the photocatalyst, ensuring even light distribution and mitigating fouling. This review not only highlights recent advancements in the removal of PFASs using photocatalysis and membrane separation but also provides comprehensive information on the integration of photocatalysis and membrane separation to form photocatalytic membrane reactors. It emphasizes the performance of immobilized and slurry systems in PFAS removal while also addressing the associated challenges and offering recommendations for improvement. Factors influencing the performance of these methods will be comprehensively discussed, as well as the nanomaterials used for each technology. Additionally, knowledge gaps regarding the removal of PFASs using integrated photocatalytic membrane systems will be addressed, along with a comprehensive discussion on how these technologies can be applied in real-world applications.

An S-scheme TiO2/g-C3N4 nanocomposite effectively degrades phenanthrene under visible light

It is a challenge to effectively degrade phenanthrene (PHE) pollutants, which are widely present in aquatic environments, in order to reduce harm to humans and ecosystems. In this study, an S-scheme TiO2/g-C3N4 photocatalytic system is constructed using 0D TiO2 nanospheres and 2D g-C3N4 nanosheets for the removal of PHE from water under sunlight irradiation. The effects of irradiation time, quality ratio of TiO2 to g-C3N4, and cycle time on the performance of the TiO2/CN photocatalyst are investigated. The experimental results show that the ratio of TiO2 to g-C3N4 significantly affects the photocatalytic activity of the photocatalyst. Under the optimal ratio of TiO2 to g-C3N4 (50 % TiO2/CN), the apparent reaction rate constant for phenanthrene reached 0.00796 min−1, which is 11.5 times higher than that of pure TiO2 (0.00069 min−1). The tests of optical performance and photoelectrochemical properties further confirmed that the construction of the TiO2/g-C3N4 S-type photocatalyst successfully enhanced the spatial separation efficiency of photogenerated carriers and ensured a continuous supply of energy during the redox reaction process. Converting highly toxic phenanthrene into a non-toxic green degradation product provides an practical strategy for the safe treatment of PHE in aqueous environments through the use of visible-light-driven heterojunction photocatalysts. Additionally, the data collected on phenanthrene degradation in this study will provide valuable references for developing degradation methods for other PAHs, such as naphthalene, anthracene, and pyrene.

Selective oxidation of benzyl alcohols photocatalyzed by asymmetric cobalt thioporphyrazine supported on alumina

The sunlight-powered transformation of alcohols to corresponding carboxylic acids offers a feasible route for fine chemical synthesis. In this work, the asymmetric cobalt tri(2,3-bis(butylthio)maleonitrile)-(1,4-dithiin) porphyrazine (CoPz(SBu)6(dtn)) was synthesized, more importantly, its single crystal was further obtained by the solvent evaporation method. Then the asymmetric CoPz(SBu)6(dtn) supported on neutral Al2O3 particles to form composite photocatalyst CoPz(SBu)6(dtn)@Al2O3, which possessed strong visible light absorption. Under simulated sunlight irradiation using a xenon lamp, the composite photocatalyst CoPz(SBu)6(dtn)@Al2O3 exhibited excellent photocatalytic activity for selective oxidation of benzyl alcohol to benzoic acid in water under conditions of green H2O2 as oxidant and K2CO3 as additive. The conversion of benzyl alcohol was up to 53.8 % together with 99 % selectivity of benzoic acid over composite photocatalyst CoPz(SBu)6(dtn)@Al2O3. Meanwhile, this photocatalytic system had feasible substrate generalizability and excellent photocatalytic activity for substituted benzyl alcohols containing both electron-donating and electron-withdrawing substituents. The composite photocatalyst CoPz(SBu)6(dtn)@Al2O3 exhibited excellent photocatalytic durability, which was confirmed by the recycling experiments. This work manifests the asymmetric thioporphyrazine as photocatalyst is feasible in implementing sunlight-powered selective transformation.

A Review: Recent Advances of Piezoelectric Photocatalysis in the Environmental Fields.

Piezoelectric photocatalysis can effectively suppress the recombination of electron holes during the course of photocatalysis, which has been widely applied in environmental and energy catalysis. Its advantage is that when the piezoelectric effect happens, a built-in electric field is formed inside the catalyst, which improves the separation efficiency of photogenerated charge carriers and obtains more excellent photocatalytic performance. The efficient conversion of mechanical energy to chemical energy can be realized through the synergistic effect of the piezoelectric effect, and photocatalysis is greatly significant in solving the energy crisis and providing environmental protection. Therefore, we organized a more complete review to better understand the mechanism and system of piezoelectric photocatalysis. We briefly introduce the principle of the piezoelectric effect, the existing types of piezoelectric photocatalysts, the practical application scenarios, and the future challenges and feasible methods to improve catalytic efficiency. The purpose of this review is to help us broaden the idea of designing piezoelectric photocatalysts, clarify the future research direction, and put it into more fields of environmental protection and energy reuse.

Photocatalytic Ammonia Decomposition Using Dye-Encapsulated Single-Walled Carbon Nanotubes

The photocatalytic decomposition of ammonia to produce N2 and H2 was achieved using single-walled carbon nanotube (SWCNT) nanohybrids. The physical modification of ferrocene-dye-encapsulated CNTs by amphiphilic C60-dendron yielded nanohybrids with a dye/CNT/C60 coaxial heterojunction. Upon irradiation with visible light, an aqueous solution of NH3 and dye@CNT/C60-dendron nanohybrids produced both N2 and H2 in a stoichiometric ratio of 1/3. The action spectra of this reaction clearly demonstrated that the encapsulated dye acted as the photosensitizer, exhibiting an apparent quantum yield (AQY) of 0.22% at 510 nm (the λmax of the dye). This study reports the first example of dye-sensitized ammonia decomposition and provides a new avenue for developing efficient and sustainable photocatalytic hydrogen production systems.

Synthesis of Self-Assembled Mesoporous ZnO Microspheres Designed for Microwave-Assisted Photocatalytic Degradation of Tetracycline.

Microwave-assisted photocatalysis offers a novel approach for degrading antibiotics, while the mechanism of enhancement of microwave-induced photocatalysis remains poorly understood. In this study, tetracycline (TC) was degraded using the method of microwave-assisted photocatalysis with a ZnO catalyst, which was synthesized by the combination of hydrothermal and calcination methods. The self-assembled mesoporous ZnO catalyst exhibited superior catalytic activity in degrading TC. It is found that the degradation efficiency of TC by the ZnO catalysts with microwave-assisted photocatalysis is 4.27 times higher than that of photocatalysis alone. Of particular significance, we found that the optical absorption range of ZnO increased and the band gap decreased when microwave was introduced into the photocatalytic system. Semi-in situ photochemical tests demonstrated that more photogenerated electron-hole pairs were detected under microwave, thus further improving the photocatalytic activity of ZnO. The separation efficiency and charge transfer efficiency of photogenerated electron-hole pairs also improved due to the increase of oxygen vacancies in the synergistic effect. Meanwhile, h+ and ·OH were the main active species in the degradation system. The mechanism of microwave-induced photocatalysis is illustrated, and an efficient way for degrading antibiotic is provided in this work.

Artificial photosynthetic system for diluted CO2 reduction in gas-solid phase

Rational design of robust photocatalytic systems to direct capture and in-situ convert diluted CO2 from flue gas is a promising but challenging way to achieve carbon neutrality. Here, we report a new type of host-guest photocatalysts by integrating CO2-enriching ionic liquids and photoactive metal-organic frameworks PCN-250-Fe2M (M = Fe, Co, Ni, Zn, Mn) for artificial photosynthetic diluted CO2 reduction in gas-solid phase. As a result, [Emim]BF4(39.3 wt%)@PCN-250-Fe2Co exhibits a record high CO2-to-CO reduction rate of 313.34 μmol g−1 h−1 under pure CO2 atmosphere and 153.42 μmol g−1 h−1 under diluted CO2 (15%) with about 100% selectivity. In scaled-up experiments with 1.0 g catalyst and natural sunlight irradiation, the concentration of pure and diluted CO2 (15%) could be significantly decreased to below 85% and 10%, respectively, indicating its industrial application potential. Further experiments and theoretical calculations reveal that ionic liquids not only benefit CO2 enrichment, but also form synergistic effect with Co2+ sites in PCN-250-Fe2Co, resulting in a significant reduction in Gibbs energy barrier during the rate-determining step of CO2-to-CO conversion.