Photocatalytic Oxidation Activity Research Articles

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 Porphyrin-Based sp2 Carbon-Conjugated covalent organic polymer containing flexible chains for efficient heterogeneous photocatalysis

Porphyrin based covalent organic polymers are excellent catalysts. Herein, a sp2 carbon linked porphyrin based organic polymer H2Pp-PDAN was designed and synthesized by co-condensation of porphyrin monomer containing flexible chains H2Pp with 1, 4-phenylenediacetonitrile PDAN. As photocatalysts, H2Pp-PDAN exhibited excellent photocatalytic performance for photocatalytic oxidative coupling of amines, and was successfully used for 15 consecutive reactions with no detectable reduction of the catalytic activity. H2Pp-PDAN showed good photocatalytic activity and excellent recyclability for photocatalytic oxidation of thioanisole to methyl phenyl sulfoxide. Mechanistic studies revealed that the photocatalytic oxidation of benzylamine coupling by H2Pp-PDAN proceeds via both energy transfer and electron transfer pathways.

A monolithic self-supporting ZnFe2O4/ZnO/ZnNi foam photocatalyst and application in the decomposition of gaseous benzene

Volatile organic compounds (VOCs) are major air pollutants which seriously affect ecological environment and pose threats to human health. In this investigation, a monolithic self-supporting ZnFe2O4/ZnO/ZNF(ZFO/ZnO/ZNF) photocatalyst was developed by in-situ growing ZnFe2O4 and ZnO on ZnNi foam (ZNF). Using benzene as a representative of the target gaseous contaminants, the optimal 5ZFO/ZnO/ZNF achieved a 99.8 % removal efficiency and 99.7 % mineralization efficiency within 20 min at an initial benzene concentration of 600 ppm under simulated sunlight irradiation. Moreover, this catalyst presents the lower ullage during gas–solid reaction, and thus enables durable recycling reuse of the photocatalyst, which still retains a 95.8 % benzene decomposition after 30th consecutive run. The mechanism studies reveal that the metal-mediated Z-type heterostructure of ZFO/ZnO/ZNF enhances rapid transportation of the photo-generated electrons and promotes redox potential, leading to the excellent photocatalytic oxidation activity and mineralization efficiency. This study highlights the potential of self-supporting monolithic metal-mediated catalysts and provides a key strategy for effective VOCs degradation.

Double nonmetal elements modified porous TiO2 homogeneous junction for efficient photocatalytic oxidation of cyclohexane

The nitrogen-doped TiO2 with mesoporous structure, anatase/rutile homogeneous junction and surface carbon species were successfully synthesized by facile hydrolysis of tetrabutyl titanate and preheating under the sealed condition, followed by a urea-aided calcination process. Interestingly, the as-obtained carbon modified TiO2 intermediates prepared by pretreating at different temperatures showed a certain photocatalytic activity for cyclohexane oxidation, and the carbon species were deposited to the surfaces of TiO2 via the Ti-O-C bond. The microstructure and photocatalytic activity of the double nonmetal elements modified porous mixed-phase TiO2 microspheres were found to depend on the preheating conditions, and nitrogen was doped into TiO2 lattice, the co-modification of nitrogen and carbon jointly improved the light absorption capacity and reduced the band gap of TiO2. The construction of a mixed-phase junction further improved the photocatalytic performance of the co-modified TiO2 compared with pure anatase or rutile TiO2. The optimal catalyst (N-TiO2-3 b) displayed efficient and stable photocatalytic performance for three cycles. When the reaction was conducted in real outdoor circumstances, the high ketone yield (206.22 μmol) and selectivity (99.92 %) were achieved. The synthetic method was simple and cheap, thus this work showed great potential for green production of fine chemicals under moderate conditions.

N-doping of β-ketoenamine based covalent organic frameworks (COFs) for enhancing photocatalytic oxidation activity

β-ketoenamine-based COFs are widely investigated due to their high stability, good crystallinity and tunable skeleton structures. Nitrogen doping is one of the effective ways to enhance the catalytic activity of COFs. Herein, N-doping of β-ketoenamine-based (0N-TP-COF, 1N-TP-COF, 2N-TP-COF) COFs were successfully constructed by the Schiff base condensation reaction between 1,3,5-tiformylphloroglucinol (TP) and p-phenylenediamine containing different numbers of nitrogen atoms. Studies showed that the as-prepared COFs exhibited more suitable electronic structure and more electron-rich active sites with the increasing of N atoms. Furthermore, the photocatalytic performance of 4-formylphenylboronic acid transformation was 0N-TP-COF (99 %, 48 h) < 1N-TP-COF (99 %, 32 h) < 2N-TP-COF (99 %, 16 h), and the photocatalytic performance of benzylamine coupling was 0N-TP-COF (99 %, 16 h) < 1N-TP-COF (99 %, 3.5 h) <2N-TP-COF (99 %, 1.5 h), respectively. Note that all N-doping COFs have excellent catalytic activity as well as stability, and 2N-TP-COF exhibits the highest catalytic activity. This work demonstrates that doping of nitrogen atoms is an effective way to enhance photocatalytic performance.

Metal alkoxides as models for metal oxides—the concept revisited

Sol-Gel synthesis of metal oxides constitutes a tremendously exciting domain of inorganic chemistry, where molecular and supramolecular science meet the physical chemistry and materials science. Structure and reactivity, especially surface complexation of biologically important molecules on the surface of metal oxide nanoparticles can efficiently be traced through structural studies of metal oxo-paperbags—the product of partial hydrolysis of alkoxide precursors. Paperbag is a recently proposed term to denote oligonuclear complexes not featuring intrinsic metal-metal bonding and thus not qualified to be called “clusters”. Another important insight, provided recently by the studies of heterometallic species, is dealing with visualization of bonding modes of single atom catalysts on metal oxide substrates and reveals possible coordination environments of heteroatoms on doping. The studies of large paperbag aggregates can contribute to understanding of factors influencing the bandgap and photocatalytic activity of related oxides. The use of these species directly as photo or electro catalysts is rather debatable, however, in the view of high reactivity of these alkoxide intermediates, easily transforming them into metal oxide nanoparticles on hydrolysis or thermolysis.Graphical

Synergistic photocatalytic activity of zinc oxide and low molecular weight chitosan nanocomposite

Synergistic photocatalytic activity of zinc oxide and low molecular weight chitosan nanocomposite

Water adsorption on ferroelectric PbTiO3 (0 0 1) surface: A density functional theory study

In this work, combining the density functional theory (DFT) calculations and the ab initio molecular dynamics (AIMD) simulations, the water adsorption behavior, including the molecular and the dissociative adsorption on the negatively polarized (0 0 1) surface of ferroelectric PbTiO3 was comprehensively studied. Our theoretical results show that the dissociative adsorption of water is more energetically favorable than the molecular adsorption on the pristine PbTiO3 (0 0 1) surface. It has been also found that introducing surface oxygen vacancies (OV) can enhance the thermodynamic stability of dissociative adsorption of water molecule. The AIMD simulations demonstrate that water molecule can spontaneously dissociate into hydrogen atoms (H) and hydroxyl groups (OH) on the pristine PbTiO3 (0 0 1) surface at room temperature. Moreover, the surface OV can effectively facilitate the dissociative adsorption of water molecules, leading to a high surface coverage of OH group, thus giving rise to a high reactivity for water splitting on defective PbTiO3 (0 0 1) surface with OV. Our results not only comprehensively understand the reason for the photocatalytic water oxidation activity of single domain PbTiO3, but also shed light on the development of high performance ferroelectric photocatalysts for water splitting.

Enhanced antibacterial and visible light driven photocatalytic activity of graphene oxide mediated Ag2O nanocomposites

Enhanced antibacterial and visible light driven photocatalytic activity of graphene oxide mediated Ag2O nanocomposites

Mesoporous g-C3N4/ZnFe2O4/TCPP nanocomposite for selective liquid-phase oxidation of alcohols to aldehydes under visible light irradiation

This study provides a viable strategy for the production of aromatic benzaldehydes by a three-component magnetic recoverable photocatalyst. The novel photocatalyst was fabricated by modification of Graphitic carbon nitride (g-C3N4) using ZnFe2O4 magnetic nanoparticles and Tetrakis(4-carboxyphenyl)porphyrin (TCPP) and labeled as CFP where C is the carbonic substrate, F shows the magnetic component and P demonstrated TCPP porphyrin. The optimized CFP photocatalyst demonstrated approximately 96 % conversion and 99 % selectivity for the oxidation of benzyl alcohol to benzaldehyde. The photocatalytic reaction carried out in the presence of acetonitrile and H2O2 as solvent and oxidant under LED lamp (15 W) irradiation. The results reveal that the values of conversion and selectivity of various types of benzylic alcohols are attributed to the aromaticity and position of substituents on the benzene ring. The reusability of CFP photocatalyst was investigated up to the fourth cycle, and it revealed any significant loss of photocatalytic oxidation activity, which is related to high structural stability of photocatalyst.

Incorporating ReS2 Nanosheet into ZnIn2S4 Nanoflower as Synergistic Z-Scheme Photocatalyst for Highly Effective and Stable Visible-Light-Driven Photocatalytic Hydrogen Evolution and Degradation.

Inspired by natural photosynthesis, the visible-light-driven Z-scheme system is very effective and promising for boosting photocatalytic hydrogen production and pollutant degradation. Here, a synergistic Z-scheme photocatalyst is constructed by coupling ReS2 nanosheet and ZnIn2S4 nanoflower and the experimental evidence for this direct Z-scheme heterostructure is provided by X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and electron paramagnetic resonance. Consequently, such a unique nanostructure makes this Z-scheme heterostructure exhibit 23.7 times higher photocatalytic hydrogen production than that of ZnIn2S4 nanoflower. Moreover, the ZnIn2S4/ReS2 photocatalyst is also very stable for photocatalytic hydrogen evolution, almost without activity decay even storing for two weeks. Besides, this Z-scheme heterostructure also exhibits superior photocatalytic degradation rates of methylene blue (1.7 × 10-2 min-1) and mitoxantrone (4.2 × 10-3 min-1) than that of ZnIn2S4 photocatalyst. The ultraviolet-visible absorption spectra, transient photocurrent spectra, open-circuit potential measurement, and electrochemical impedance spectroscopy reveal that the superior photocatalytic performance of ZnIn2S4/ReS2 heterostructure is mostly attributed to its broad and strong visible-light absorption, effective separation of charge carrier, and improved redox ability. This work provides a promising nanostructure design of a visible-light-driven Z-scheme heterostructure to simultaneously promote photocatalytic reduction and oxidation activity.

Photocatalytic oxidation of methane to C1 oxygenates promoted by Fe−N−Ti electron bridge

Highly efficient oxidation of methane (CH4) to liquid oxygenates with O2 over non-noble heterogeneous catalysts under mild conditions remains a huge challenge owing to the ultra-inert C−H bond of CH4 molecule. In this work, we have successfully constructed photocatalysts of N-Fe2Ti3O9/TiO2 by thermal treatment of a bimetallic amino-functionalized metal-organic framework, i.e., Fe-NH2-MIL-125, aiming at photocatalytic oxidation of CH4 to one-carbon (C1) oxygenates using O2 at room temperature. Impressively, the optimized photocatalyst of 10 wt%N-Fe2Ti3O9/TiO2 exhibited superior activity in photocatalytic oxidation of CH4 with a formation rate of C1 liquid oxygenates of 5897 μmol·gcat.–1·h–1. The selectivity of the primary products (CH3OH and CH3OOH) was up to 91.7 % over 10 wt%N-Fe2Ti3O9/TiO2. Mechanistic studies demonstrated that the presence of Fe−N−Ti electron bridge could trigger robust charge redistribution in 10 wt%N-Fe2Ti3O9/TiO2 to form electron-deficient Fe sites and electron-rich Ti sites. The formed electron-deficient Fe sites could oxidize H2O molecules to ·OH radicals. Meanwhile, electron-rich Ti sites greatly enhanced the chemisorption and activation of CH4 molecules, thereby synergistically promoting the generation of C1 liquid oxygenates.

Visible light-driven removal of Rhodamine B using indium-doped zinc oxide prepared by sol–gel method

Industrial dye contamination in wastewater poses significant environmental challenges, necessitating the development of efficient photocatalysts for degradation. In this work, we investigate the In doping effect in the photocatalytic activity of zinc oxide (ZnO) nanoparticles for effective RhB degradation. Indium-doped ZnO nanoparticles were synthesized via sol–gel method and x-ray diffraction (XRD) analysis revealed a wurtzite hexagonal structure, with the crystallite size being varying from 65 nm to 53 nm with the introduction of In content. XPS measurements on the 3% In-doped ZnO sample revealed distinct core level spectra for In 3d, Zn 2p, and O 1s regions, confirming the presence of indium, zinc, and oxygen. Brunauer–Emmett–Teller (BET) analysis revealed increased surface area and pore size, with specific surface areas escalating from 0.9 m²/g for pure ZnO to 10.1 m²/g for 3% indium-doped ZnO. Photocatalytic experiments exhibited significant RhB degradation, with degradation efficiencies reaching 93% for 3% indium-doped ZnO under visible light irradiation due to the effect of the presence of In, which causing light absorption enhancement, narrow the band gap and improve charge carrier separation. These findings underscore the potential of indium-doped ZnO nanoparticles as efficient and sustainable photocatalysts for wastewater treatment, offering a promising avenue to address environmental challenges associated with industrial dye-contaminated effluents.Graphical

Pyrene‐Alkyne‐Based Conjugated Porous Polymers with Skeleton Distortion‐Mediated ⋅O2− and 1O2 Generation for High‐Selectivity Organic Photosynthesis

AbstractReactive oxygen species (ROS) play a crucial role in determining photocatalytic reaction pathways, intermediate species, and product selectivity. However, research on ROS regulation in polymer photocatalysts is still in its early stages. Herein, we successfully achieved series of modulations to the skeleton of Pyrene‐alkyne‐based (Tetraethynylpyrene (TEPY)) conjugated porous polymers (CPPs) by altering the linkers (1,4‐dibromobenzene (BE), 4,4′‐dibromobiphenyl (IP), and 3,3′‐dibromobiphenyl (BP)). Experiments combined with theoretical calculations indicate that BE‐TEPY exhibits a planar structure with minimal exciton binding energy, which favors exciton dissociation followed by charge transfer with adsorbed O2 to produce ⋅O2−. Thus BE‐TEPY shows optimal photocatalytic activity for phenylboronic acid oxidation and [3+2] cycloaddition. Conversely, the skeleton of BP‐TEPY is significantly distorted. Its planar conjugation decreases, intersystem crossing (ISC) efficiency increases, which makes it more prone for resonance energy transfer to generate 1O2. Therefore, BP‐TEPY displays best photocatalytic activity in [4+2] cycloaddition and thioanisole oxidation. Both above reactant conversion and its product selectivity exceed 99 %. This work systematically reveals the intrinsic structure–activity relationship among the skeleton structure of CPPs, excitonic behavior, and selective generation of ROS, providing new insights for the rational design of highly efficient and selective CPPs photocatalysts.

Pyrene-Alkyne-Based Conjugated Porous Polymers with Skeleton Distortion-Mediated ⋅O2 - and 1O2 Generation for High-Selectivity Organic Photosynthesis.

Reactive oxygen species (ROS) play a crucial role in determining photocatalytic reaction pathways, intermediate species, and product selectivity. However, research on ROS regulation in polymer photocatalysts is still in its early stages. Herein, we successfully achieved series of modulations to the skeleton of Pyrene-alkyne-based (Tetraethynylpyrene (TEPY)) conjugated porous polymers (CPPs) by altering the linkers (1,4-dibromobenzene (BE), 4,4'-dibromobiphenyl (IP), and 3,3'-dibromobiphenyl (BP)). Experiments combined with theoretical calculations indicate that BE-TEPY exhibits a planar structure with minimal exciton binding energy, which favors exciton dissociation followed by charge transfer with adsorbed O2 to produce ⋅O2 -. Thus BE-TEPY shows optimal photocatalytic activity for phenylboronic acid oxidation and [3+2] cycloaddition. Conversely, the skeleton of BP-TEPY is significantly distorted. Its planar conjugation decreases, intersystem crossing (ISC) efficiency increases, which makes it more prone for resonance energy transfer to generate 1O2. Therefore, BP-TEPY displays best photocatalytic activity in [4+2] cycloaddition and thioanisole oxidation. Both above reactant conversion and its product selectivity exceed 99 %. This work systematically reveals the intrinsic structure-activity relationship among the skeleton structure of CPPs, excitonic behavior, and selective generation of ROS, providing new insights for the rational design of highly efficient and selective CPPs photocatalysts.

Remarkable improvement in photocatalytic activity of g-C3N4 for NO oxidation through surface hydroxylation

The nitrogen oxide emissions originating from combustion pose significant risks to the environment. Photocatalysis is considered an efficient and environmentally friendly strategy to alleviate this problem. Graphitic carbon nitride (g-C3N4) is regarded as one of the most promising organic photocatalytic materials for environmental purification. However, its small specific surface area, weak adsorption and high recombination rate of charge carriers result in low intrinsic photocatalytic activity. To overcome these obstacles, a hydrothermal treatment of dicyandiamide-derived g-C3N4 (DCN) at different temperatures (140–200 °C) was employed to enhance the photocatalytic activity for NO oxidation. The experimental results demonstrated a significant improvement in the photocatalytic oxidation removal rate of NO after a hydrothermal treatment. The optimal photocatalyst, DCN-180, treated at 180 °C, demonstrated the highest NO removal efficiency (65.0 %), which is twice the value of pristine DCN (32.5 %). Additionally, the formation of the toxic intermediate NO2 was effectively suppressed during the reaction. Photoelectrochemical tests revealed that DCN-180 exhibited higher photocurrent density and smaller impedance radius compared to the untreated g-C3N4 sample. Moreover, density functional theory (DFT) calculations confirmed that the DCN-180 sample showed a stronger ability to adsorb O2 and NO. The enhanced photocatalytic NO oxidation performance of DCN-180 has been primarily attributed to its enlarged specific surface area (from 10.7 to 35.5 m2 g−1), local polarization effect, reduced interfacial charge transfer resistance, and improved adsorption abilities for NO and O2 molecules. This study provides valuable insights for designing and preparing highly efficient g-C3N4 based photocatalysts through surface modification for photocatalytic NO purification.

Deciphering the effect of calcination temperature on crystallinity, morphology, oxygen vacancy and photocatalytic activity of bi-phasic ZnO/ZnCo2O4 heterostructured nanomaterials

This study investigates the synthesis of cobalt incorporated zinc oxide (ZnO) metal oxide via co-precipitation followed by calcination at varying temperatures ranging from 300 °C to 700 °C. X-ray diffraction analysis revealed the presence of two crystallite phases, hexagonal ZnO and wurtzite ZnCo2O4, at temperatures between 500 °C and 700 °C, while only the ZnO phase was observed below 500 °C with ZnCo2O4 remaining amorphous. Morphological evolution revealed the gradual development of a rod-shaped morphology for ZnO phase, reaching peak stability at 500 °C, beyond which the structural rupture occurred. The impact of temperature on oxygen vacancy, surface area, optical band gap energy, and recombination of charge carriers was investigated. Photocatalytic activity against MO dye demonstrated an increase with calcination temperature up to 500 °C, attributed to improved crystallinity. Notably, the sample annealed at 500 °C exhibited the highest photocatalytic activity due to its highly ordered crystallinity, bi-phase composition, and appropriate band gap. However, further increase in calcination temperature led to a rapid decrease in photocatalytic activity due to morphological destruction and loss of crystallinity. These findings highlight the importance of optimizing calcination temperature to tailor the crystallinity, morphology, and photocatalytic activity of mixed metal oxides, offering insights for controlled material synthesis with desired properties.

Rational design of g-C3N4-based photocatalysts with intramolecular donor-acceptor structures for deep oxidation of emerging organic micropollutants

An in-situ route for the fabrication of intramolecular electron donor-acceptor (D-A) structured g-C3N4 photocatalysts is developed by the preorganization of urea with the precursor of electron donor units, such as 4-iodobenzaldehyde, 5-bromo-2-thiophenaldehyde and 5-bromo-2-furaldehyde, followed by thermal polymerization. In the resulting benzene unit-, thiophene unit- and furan unit-based D-A structured g-C3N4 photocatalysts, namely, BHCNx, SCNx, and OCNx, the incorporated electron donor units (i.e., benzene units, thiophene units and furan units) link with the electron acceptors (i.e., heptazine units) through CN and CN covalent bonds. In comparison of bulk g-C3N4, all D-A structured g-C3N4 display notably enhanced visible-light photocatalytic oxidation activity in the degradation of emerging organic micropollutants, p-nitrophenol (PNP) and methylparaben (MPB), in which the apparent first-order kinetic constant of the optimized BHCN2, SCN2, and OCN2 is 1.6, 3.0 and 6.8 times higher than bulk g-C3N4 for PNP degradation and 1.9, 3.4 and 2.6 times higher than bulk g-C3N4 for MPB degradation. Importantly, the micropollutants can be not only degraded but also mineralized completely. The catalysts are also robust in the removal of mixed emerging organic micropollutants in pharmaceutical wastewater, exhibiting potential of dealing with organic micropollutants in wastewater. Mechanism studies reveal that the unique intramolecular charge transfer process in the catalysts enhances visible-light harvesting capacity, boosts directional transfer of the photogenerated charges and increases adsorption towards oxygen molecules. These collective improvements can maximum utilization the photogenerated electrons and holes to yield plentiful reactive oxygen species for deep oxidization of the pollutants.

Novel defect-transit dual Z-scheme heterojunction: Sulfur-doped carbon nitride nanotubes loaded with bismuth oxide and bismuth sulfide for efficient photocatalytic amine oxidation

The rational design of Z-scheme heterojunction hybrid photocatalysts is considered a promising way to achieve high photocatalytic activity. In this study, a dual Z-scheme heterojunction with bismuth sulfide (Bi2S3) nanorods and bismuth oxide (Bi2O3) nanoparticles anchored Sulfur-doped carbon nitride (S-CN) nanotubes (Bi2S3/S-CN/Bi2O3) is designed and fabricated through the ordinal metal ion adsorption, pyrolysis, and sulfidation processes using supramolecular rods as precursor. Compared with pristine Bi2S3, Bi2O3, and CN, the dual Z-scheme tube-shaped Bi2S3/S-CN/Bi2O3 catalyst exhibited a significantly improved photocatalytic activity in amine oxidation. The optimized Bi2S3/S-CN/Bi2O3 nanostructure exhibits a 97.6 % benzylamine conversion and 99.4 % imine selectivity within 4 h under simulated solar light irradiation. The excellent activity of Bi2S3/S-CN/Bi2O3 nanotubes can be attributed to the characteristic hollow defect band structure and efficient charge separation and transfer achieved by the dual Z-scheme charge transfer mechanism, which was systematically studied using electron spin resonance spectroscopy, Kelvin probe force microscope, and other techniques. The optimized dual Z-scheme heterojunction hybrid photocatalyst maintains the high oxidizing ability of Bi2S3 and Bi2O3 and the excellent reducing ability of CN, thereby significantly enhancing the photocatalytic activity. This research provides a facile and feasible synthesis strategy for designing dual Z-scheme heterojunctions with defect band structure to improve the photocatalytic activity.

Investigating the Electronic Properties and Stability of Rh3 Clusters on Rutile TiO2 for Potential Photocatalytic Applications.

Addressing the pressing needs for alternatives to fossil fuel-based energy sources, this research explores the intricate interplay between Rhodium (Rh3) clusters and titanium dioxide (TiO2) to improve photocatalytic water splitting for the generation of eco-friendly hydrogen. This research applies the density functional theory (DFT) coupled with the Hartree-Fock theory to meticulously examine the structural and electronic structures of Rh3 clusters on TiO2 (110) interfaces. Considering the photocatalytic capabilities of TiO2 and its inherent limitations in harnessing visible light, the potential for metals such as Rh3 clusters to act as co-catalysts is assessed. The results show that triangular Rh3 clusters demonstrate remarkable stability and efficacy in charge transfer when integrated into rutile TiO2 (110), undergoing oxidation in optimal adsorption conditions and altering the electronic structures of TiO2. The subsequent analysis of TiO2 surfaces exhibiting defects indicates that Rh3 clusters elevate the energy necessary for the formation of an oxygen vacancy, thereby enhancing the stability of the metal oxide. Additionally, the combination of Rh3-cluster adsorption and oxygen-vacancy formation generates polaronic and localized states, crucial for enhancing the photocatalytic activity of metal oxide in the visible light range. Through the DFT analysis, this study elucidates the importance of Rh3 clusters as co-catalysts in TiO2-based photocatalytic frameworks, paving the way for empirical testing and the fabrication of effective photocatalysts for hydrogen production. The elucidated impact on oxygen vacancy formation and electronic structures highlights the complex interplay between Rh3 clusters and TiO2 surfaces, providing insightful guidance for subsequent studies aimed at achieving clean and sustainable energy solutions.