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Constructing heterojunction of supramolecular arrays self-assembled on metal-organic frameworks (MOFs) with elaborate charge transfer mechanisms is a promising strategy for the photocatalytic oxidation of organic pollutants. Herein, H12 SubPcB-Br (SubPc-Br) and UiO-66 are used to obtain the step-scheme (S-scheme) heterojunction SubPc-Br/UiO-66 for the first time, which is then applied in the photocatalytic oxidation of minocycline. Atomic-level B-O-Zr charge-transfer channels and van der Waals force connections synergistically accelerated the charge transfer at the interface of the SubPc-Br/UiO-66 heterojunction, while the establishment of the B-O-Zr bonds also led to the directional transfer of charge from SubPc-Br to UiO-66. The synergy is the key to improving the photocatalytic activity and stability of SubPc-Br/UiO-66, which is also verified by various characterization methods and theoretical calculations. The minocycline degradation efficiency of supramolecular SubPc-Br/UiO-66 arrays reach 90.9% within 30 min under visible light irradiation. The molecular dynamics simulations indicate that B-O-Zr bonds and van der Waals force contribute significantly to the stability of the SubPc-Br/UiO-66 heterojunction. This work reveals an approach for the rational design of semiconducting MOF-based heterojunctions with improved properties.
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Recent trends in addressing the impending water crisis focus on the development of innovative water treatment methods. This work utilizes pollen as a core template to synthesize highly efficient onion-like photocatalysts for pollutant mineralization. The study showcases a novel electrochemical synthesis method that maintains the structural integrity of pollen, resulting in increased surface area and enhanced photocatalytic activity. After 90-min of visible light irradiation, over 99% mineralization is achieved. These hybrid photocatalysts demonstrate exceptional stability and efficacy in degrading pollutants. The used photocatalysts can be recycled into biopellets with an ash content of less than 7% (weight), moisture content of less than 8% (weight), and a calorific value of ≈22.1 ± 0.3 MJ kg-1. Additionally, the resulting ashes serve as effective peroxymonosulphate activators for pollutant mineralization. This process offers sustainable waste management while minimizing waste production, providing a practical solution for water purification. The efficacy of this approach in pollutant removal is underscored by mineralization rates exceeding 99%.
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The coupling of photocatalytic hydrogen production and selective oxidation of benzylamine is a topic of significant research interest. However, enhancing the bifunctional photocatalytic activity in this context is still a major challenge. The construction of Z-scheme heterojunctions is an effective strategy to enhance the activity of bifunctional photocatalysts. Herein, a p-n type direct Z-scheme heterojunction CuS/TiO2 is constructed using metal-organic framework (MOF)-derived TiO2 as a substrate. The carrier density is measured by Mott-Schottky under photoexcitation, which confirms that the Z-scheme electron transfer mode of CuS/TiO2 is driven by the diffusion effect caused by the carrier concentration difference. Benefiting from efficient charge separation and transfer, photogenerated electrons, and holes are directedly transferred to active oxidation and reduction sites. CuS/TiO2 also exhibits excellent bifunctional photocatalytic activity without noble metal cocatalysts. Among them, the H2 evolution activity of the CuS/TiO2 is found to be 17.1 and 29.5 times higher than that of TiO2 and CuS, respectively. Additionally, the yields of N-Benzylidenebenzylamine (NBB) are 14.3 and 47.4 times higher than those of TiO2 and CuS, respectively.
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Long-term exposure to low concentration indoor VOCs of acetaldehyde (CH3CHO) is harmful to human health. Thus, a novel isogenous heterojunction CeO2/Ce-MOF photocatalyst is synthesized via a one-step hydrothermal method for the effective elimination of CH3CHO in this work. This CeO2/Ce-MOF photocatalyst performs well in CH3CHO removal and achieves an apparent quantum efficiency of 7.15% at 420 nm, which presents ≈6.7 and 3.4 times superior to those generated by CeO2 and Ce-MOF, respectively. The enhanced efficiency is due to two main aspects including i) an effective photocarrier separation ability and the prolonged reaction lifetime of excitons play crucial roles and ii) the formation of an internal electric field (IEF) is sufficient to overcome the considerable exciton binding energy, and increases the exciton dissociation efficiency by up to 50.4%. Moreover, the reasonable pathways and mechanisms of CH3CHO degradation are determined by in situ DRIFTS analysis and simulated DFT calculations. Those results demonstrated that S-scheme heterojunction successfully increases the efficiency of harmful volatile organic compounds elimination, and it offers essential guidance for designing rare earth-based MOF photocatalysts.
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Efficient artificial photosynthesis of disulfide bonds holds promises to facilitate reverse decoding of genetic codes and deciphering the secrets of protein multilevel folding, as well as the development of life science and advanced functional materials. However, the incumbent synthesis strategies encounter separation challenges arising from leaving groups in the âSâSâ coupling reaction. In this study, according to the reaction mechanism of free-radical-triggered âSâSâ coupling, light-driven heterojunction functional photocatalysts are tailored and constructed, enabling them to efficiently generate free radicals and trigger the coupling reaction. Specifically, perovskites and covalent organic frameworks (COFs) are screened out as target materials due to their superior light-harvesting and photoelectronic properties, as well as flexible and tunable band structure. The in situ assembled Z-scheme heterojunction MAPB-M-COF (MAPbBr3 = MAPB, MA+ = CH3 NH2 + ) demonstrates a perfect trade-off between quantum efficiency and redox chemical potential via band engineering management. The MAPB-M-COF achieves a 100% âSâSâ coupling yield with a record photoquantum efficiency of 11.50% and outstanding cycling stability, rivaling all the incumbent similar reaction systems. It highlights the effectiveness and superiority of application-oriented band engineering management in designing efficient multifunctional photocatalysts. This study demonstrates a concept-to-proof research methodology for the development of various integrated heterojunction semiconductors for light-driven chemical reaction and energy conversion.
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Metal-free organic photocatalysts for photo-mediated reversible deactivation radical polymerization (photo-RDRP) are witnessed to make increasing advancement in the precise synthesis of polymers. However, challenges still exist in the development of high-efficiency and environmentally sustainable carbon dots (CDs)-based organocatalysts. Herein, N-doped CDs derived from phenanthroline derivative (Aphen) are prepared as metal-free photocatalysts for photoinduced electron transfer reversible addition-fragmentation chain transfer (PET-RAFT) polymerization. The introduction of phenanthroline structure enhances the excited state lifetime of CDs and expands the conjugated length of their internal structure to enable the light-absorption to reach green light region, thereby enhancing photocatalytic activity. The as-designed CDs exhibit unprecedented photocatalytic capacity in photopolymerization even in large-volume reaction (100 mL) with high monomer conversion and narrow polymer dispersity (Mw/Mn < 1.20) under green light. The photocatalytic system is compatible with PET-RAFT polymerization of numerous monomers and the production of high molecular weight polyacrylate (Mn >250 000) with exquisite spatiotemporal control. Above results confirm the potential of CDs as photocatalyst, which has not been achieved with other CDs catalysts used in photo-RDRP. In addition, the construction of fluorescent polymer nanoparticles using CDs as both photocatalyst and phosphor through photoinitiated polymerization-induced self-assembly (Photo-PISA) technology is successfully demonstrated for the first time.
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The exaltation of light-harvesting efficiency and the inhibition of fast charge recombination are pivotal to the improvement of photoelectrochemical (PEC) performance. Herein, a direct Z-scheme heterojunction is designed of Cu2S/CdIn2S4 by in situ growth of CdIn2S4 nanosheets on the surface of hollow CuS cubes and then annealing at 400 °C. The constructed Z-scheme heterojunction is demonstrated with electron paramagnetic resonance and redox couple (p-nitrophenol/p-aminophenol) measurements. Under illumination, it shows the photocurrent 6 times larger than that of hollow Cu2S cubes, and affords outstanding PEC performance over the known Cu2S and CdIn2S4-based photocatalysts. X-ray photoelectron spectroscopy and density functional theory results demonstrate a strong internal electric field formed in Cu2S/CdIn2S4 Z-scheme heterojunction, which accelerates the Z-scheme charge migration, thereby promoting electron-hole separation and enhancing their utilization efficiency. Moreover, the hollow structure of Cu2S is conducive to shortening the charge transport distance and improving light-harvesting capability. In proof-of-concept PEC application, a PEC detection method for miRNA-141 based on the sensitivity of benzo-4-chloro-hexadienone to light absorption on Cu2S/CdIn2S4 modified electrode is developed with good selectivity and a limit of detection of 32 aM. This work provides a simple approach for designing photoactive materials with highly efficient PEC performance.
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Semiconductor photocatalysis has great potential in the fields of solar fuel production and environmental remediation. Nevertheless, the photocatalytic efficiency still constrains its practical production applications. The development of new semiconductor materials is essential to enhance the solar energy conversion efficiency of photocatalytic systems. Recently, the research on enhancing the photocatalytic performance of semiconductors by introducing bismuth (Bi) has attracted widespread attention. In this review, we briefly overview the main synthesis methods of Bi/semiconductor photocatalysts and summarize the control of the micromorphology of Bi in Bi/semiconductors and the key role of Bi in the catalytic system. In addition, the promising applications of Bi/semiconductors in photocatalysis, such as pollutant degradation, sterilization, water separation, CO2 reduction, and N2 fixation, are outlined. Finally, an outlook on the challenges and future research directions of Bi/semiconductor photocatalysts is given. We aim to offer guidance for the rational design and synthesis of high-efficiency Bi/semiconductor photocatalysts for energy and environmental applications.
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A novel, rapid, and facile method for one-step sonoelectrochemical synthesis of zinc oxide nanoparticles (UEZ) was introduced in this study. The optimum operating parameters have been selected at a voltage of 7.5 V, KCl concentration of 0.5 M, and the reaction time of 60 min. The as-prepared UEZ were characterized by XRD, SEM, and HRTEM. It was found that the UEZ has a hexagonal wurtzite structure with high crystalline quality, good purity, a size range of 30-100 nm, and good photocatalytic degradation of methylene blue. This work provides a facile route for large-scale synthesizing ZnO nanoparticles via anodization.
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The poor light absorption and low carrier separation efficiency of Titanium dioxide (TiO2) limit its further application. The introduction of plasma metal Ag have the potential to solve these drawbacks owing to its plasma resonance effect. Thus core-shell structure Ag@TiO2 plasma photocatalysts was prepared by using facile reduction method in this work. More specifically, Ag@TiO2 composite catalysts with different Ag loading amounts were prepared in the presence of surfactant PVP. Ag@TiO2 demonstrates excellent light absorption performance and photoelectric separation efficiency compared with pure TiO2. As a result, it displays excellent performance of Cr(VI) reduction under visible light. The optimal composite catalysts Ag@TiO2-5P achieves exceptional visible-light-driven photocatalytic Cr(VI) reduction efficiency of 0.01416 min-1 that is 2.29 times greater than pure TiO2. To investigate the role of PVP, we also synthesized Ag@TiO2-5 without PVP. The experimental results show that although Ag@TiO2-5 Cr(VI) reduction performance is superior to pure TiO2, it significantly decreases compared with Ag@TiO2-5P. The results of TEM and optoelectronic testing show that agglomeration of Ag particles leads to a decrease in the photoelectric separation efficiency of Ag@TiO2-5. The smaller Ag particles provide more active sites and demonstrating a stronger overall local surface plasmon resonance (LSPR) effect. DMPO spin-trapping ESR spectra testing indicates that âO2- and âOH are the main reactive species. This research provides a potential strategy to prepare Ag-based plasma photocatalysts for environment protection.
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Prata , Ressonância de Plasmônio de Superfície , Prata/química , Titânio/química , Cromo/química , Luz , CatáliseRESUMO
This review approach is divided into two scopes to focus the pollution threats. We cover the applications of nanomaterials to curtail the pollution induced by fossil fuel combustion, and textile dye effluents. Toxic emissions released from automobile exhaust that comprise of NOX. SOX and PAHs compile to harsh breathing and respiratory troubles. The effluents generated from the mammoth textile and leather industry is potential threat to beget massive health issues to human life, and environmental problem. Part I projects the broad envisage on role of nano materials in production of alternative biofuels. In addition, green sources for synthesizing nanomaterials are given special importance. Nano catalyst's utilization in bio-derived fuels such as biogas, bio-oil, bioethanol, and biodiesel are catered to this article. Part II cover the current statistics of textile effluent pollution level in India and its steps in confronting the risks of pollution are discussed. A clear picture of the nano techniques in pre-treatment, and the recent nano related trends pursued in industries to eliminate the dyes and chemicals from the discharges is discussed. The substantial aspect of nano catalysis in achieving emission-free fuel and toxic-free effluents and the augmentation in this field is conferred. This review portrays the dependency on nano materials & technology for sustainable future.
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Combustíveis Fósseis , Nanoestruturas , Indústria Têxtil , Nanoestruturas/química , Combustíveis Fósseis/análise , Resíduos Industriais/análise , Têxteis/análise , Biocombustíveis/análiseRESUMO
Plastic pollution has become a major environmental problem because it does not break down and poses risks to ecosystems and human health. This study focuses on the environmentally friendly synthesis of ZnO nanocubes using an extract from Ceropegia omissa H. Huber plant leaves. The primary goal is to investigate the viability of these nanocubes as visible-light photocatalysts for the degradation of bisphenol A (BPA). The synthesized ZnO nanocubes have a highly crystalline structure and a bandgap of 3.1 eV, making them suitable for effective visible-light photocatalysis. FTIR analysis, which demonstrates that the pertinent functional groups are present, demonstrates the chemical bonding and reducing processes that take place in the plant extract. The XPS method also studies zinc metals, oxygen valencies, and binding energies. Under visible light irradiation, ZnO nanocubes degrade BPA by 86% in 30 min. This plant-extract-based green synthesis method provides a long-term replacement for traditional procedures, and visible light photocatalysis has advantages over ultraviolet light. The study's results show that ZnO nanocubes may be good for the environment and can work well as visible light photocatalysts to break down organic pollutants. This adds to what is known about using nanoparticles to clean up the environment. As a result, this study highlights the potential of using environmentally friendly ZnO nanocubes as a long-lasting and efficient method of reducing organic pollutant contamination in aquatic environments.
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Compostos Benzidrílicos , Luz , Fenóis , Extratos Vegetais , Poluentes Químicos da Água , Óxido de Zinco , Óxido de Zinco/química , Compostos Benzidrílicos/química , Fenóis/química , Fenóis/análise , Extratos Vegetais/química , Poluentes Químicos da Água/química , Catálise , Química Verde/métodos , FotóliseRESUMO
Photocatalysis has been widely used as one of the most promising approaches to remove various pollutants in liquid or gas phases during the last decade. The main emphasis of the study is on the synergy of vacancy engineering and heterojunction formation, two widely used modifying approaches, to significantly alter photocatalytic performance. The vacancy-induced Ag2CO3/BiOBr/WO3-x heterojunction system has been fabricated using a co-precipitation technique to efficiently abate methylene blue (MB) dye and doxycycline (DC) antibiotic. The as-fabricated Ag2CO3/BiOBr/WO3-x heterojunction system displayed improved optoelectronic characteristic features because of the rational combination of dual charge transferal route and defect modulation. The Ag2CO3/BiOBr/WO3-x system possessed 97% and 74% photodegradation efficacy for MB and DC, respectively, with better charge isolation and migration efficacy. The ternary photocatalyst possessed a multi-fold increase in the reaction rate for both MB and DC, i.e., 0.021 and 0.0078 min-1, respectively, compared to pristine counterparts. Additionally, more insightful deductions about the photodegradation routes were made possible by the structural investigations of MB and DC using density functional theory (DFT) simulations. This study advances the understanding of the mechanisms forming visible light active dual Z-scheme heterojunction for effective environmental remediation.
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Providing safe access to water and addressing the impact of waterborne diseases, which claim over two million lives annually, is a major contribution to water purification. The study introduces a novel nanocomposite, Ch/Fe3O4/α-MoO3, which exhibits outstanding photocatalytic efficacy under visible light. An in-depth investigation of the nanocomposite's synthesis, characterization, and photodegradation mechanisms reveals its outstanding capabilities. Photocatalytic activity is influenced by the catalytic dose, pH, dye concentration, and reaction time, according to the study. A response surface method is used to determine the optimal conditions for Rhodamine B degradation, which results in 96.3% removal efficiency at pH 8.5, dye concentration 25 mg/L, nanocomposite dose at 22 mg/L, and reaction time 50 min. As a result of its high surface area, biocompatibility, availability, and magnetization with iron compounds, Chitosan is an excellent substrate for enhancing the photocatalytic properties of MoO3 nanoparticles. A nanocomposite with an energy band of 3.18 eV exhibits improved visible light absorption. This study confirms the nanocomposite's recyclability and stability, affirming its practicality. Besides dye removal, it offers hope for the global quest for clean water sources by addressing a broader range of waterborne contaminants. By combining molybdenum and magnetite, nanocomposite materials facilitate the degradation of pollutant and bacteria, contributing positively to society's quest for clean and safe water. It emphasizes the role nanotechnology plays in preserving human health and well-being in combating waterborne diseases.
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Luz , Nanocompostos , Rodaminas , Águas Residuárias , Poluentes Químicos da Água , Rodaminas/química , Nanocompostos/química , Poluentes Químicos da Água/química , Águas Residuárias/química , Catálise , Purificação da Água/métodos , Fotólise , Corantes/química , Molibdênio/químicaRESUMO
Photocatalysis was an attractive strategy that had potential to tackle the Microcystin-LR (MC-LR) contamination of aquatic ecosystems. Herein, magnetic photocatalyst Fe3O4/Bi2WO6/Reduced graphene oxide composites (Bi2WO6/Fe3O4/RGO) were employed to degrade MC-LR. The removal efficiency and kinetic constant of the optimized Bi2WO6/Fe3O4/RGO (Bi2WO6/Fe3O4-40%/RGO) was 1.8 and 2.3 times stronger than the pure Bi2WO6. The improved activity of Bi2WO6/Fe3O4-40%/RGO was corresponded to the expanded visible light adsorption ability and reduction of photogenerated carrier recombination efficiency through the integration of Bi2WO6 and Fe3O4-40%/RGO. The MC-LR removal efficiency exhibited a positive tendency to the initial density of algae cells, fulvic acid, and the concentration of MC-LR decreased. The existed anions (Cl-, CO3-2, NO3-, H2PO4-) reduced MC-LR removal efficiency of Bi2WO6/Fe3O4-40%/RGO. The Bi2WO6/Fe3O4-40%/RGO could degrade 79.3% of MC-LR at pH = 7 after 180 min reaction process. The trapping experiments and ESR tests confirmed that the h+, âOH, and âO2- played a significant role in MC-LR degradation. The LC-MS/MS result revealed the intermediates and possible degradation pathways.
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Bismuto , Grafite , Luz , Toxinas Marinhas , Microcistinas , Microcistinas/química , Microcistinas/efeitos da radiação , Grafite/química , Bismuto/química , Poluentes Químicos da Água/química , Fotólise , CatáliseRESUMO
The need for sunlight chemical renewal and contemporary organic transformation has fostered the advancement of environmentally friendly photocatalytic techniques. For the first time, we report on the novel crafting of a bright future with selenium-infused Eosin-B (Sein-E-B) nanocomposite photocatalysts in this work. The Sein-E-B nanocomposite materials were created using a hydrothermal process for solar chemical regeneration and organic transformation under visible light. The synthesized samples were subjected to UV-DRS-visible spectroscopy, FT-IR, SEM, EDX, EIS and XRD analysis. The energy band gap of the Sein-E-B nanocomposite photocatalyst was measured using UV-DRS, and the result was around 2.06â eV. to investigate the generated Sein-E-B catalytic activity as a nanocomposite for 1,4-NADH/NADPH re-formation and C-N bond activation. This novel photocatalyst offers a promising alternative for the regeneration of solar chemicals and C-N bond creation between pyrrole and aryl halides.
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Nanocompostos , Catálise , Estrutura Molecular , Nanocompostos/química , Processos Fotoquímicos , Selênio/químicaRESUMO
In this study, we proposed a novel imaging technique, photoinduced electrogenerated chemiluminescence microscopy (PECLM), to monitor redox reactions driven by hot carriers on single gold nanoparticles (AuNPs) on TiO2. Under laser irradiation, plasmon-generated hot carriers were separated by an electric field, leaving hot holes on the surface of AuNPs to drive ECL reactions. PECL intensity was highly sensitive to the number of hot carriers. Through quantitative image analysis, we found that PECL density on individual AuNPs decreased significantly with an increase in particle diameter, indicating that particle size has a significant impact on photoelectrochemical conversion efficiency. For the first time, we verified the feasibility of PECLM in mapping the catalytic activity of single photocatalysts. PECLM opens a new prospect for the in situ imaging of photocatalysis in a high-throughput way, which not only facilitates the optimization of plasmonic photocatalysts but also contributes to the dynamic study of photocatalytic processes on micro/nanointerfaces.
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With the introduction of single atoms in photocatalysis, a small change in the electronic and geometric structure of the substrate can result in higher energy conversion efficiency, whereas the underlying microscopic dynamics are rarely illustrated. Here, employing real-time time-dependent density functional theory, we explore the ultrafast electronic and structural dynamics of single-atom photocatalysts (SAPCs) in water splitting at the microscopic scale. The results demonstrate that a single-atom Pt loaded on graphitic carbon nitride greatly promotes photogenerated carriers compared to traditional photocatalysts, and effectively separates the excited electrons from holes, prolonging the lifetime of the excited carriers. The flexible oxidation state (Pt2+, Pt0, or Pt3+) renders the single atom as an active site to adsorb the reactant and to catalyze the reactions as a charge transfer bridge at different stages during the photoreaction process. Our results offer deep insights into the single-atom photocatalytic reactions and benefit the design of high-efficiency SAPCs.
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This work aimed to develop organic photocatalysts (PCs) that could mediate organocatalytic atom transfer radical polymerization (O-ATRP) under visible light. Through the core-modification of known chromophoric structures and ring-locking to reach a conjugation extension, annulated N-aryl benzo[kl]acridines were identified as effective visible light-responsive photocatalysts. The corresponding selenium-doped structure showed excellent performance in the O-ATRP of methacrylates, which could afford polymer products with controlled molecular weights and low dispersities under the irradiation of visible light at a 100 ppm catalyst loading.
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Harnessing solar energy to produce hydrogen through semiconductor-mediated photocatalytic water splitting is a promising avenue to address the challenges of energy scarcity and environmental degradation. Ever since Fujishima and Honda's groundbreaking work in photocatalytic water splitting, titanium dioxide (TiO2) has garnered significant interest as a semiconductor photocatalyst, prized for its non-toxicity, affordability, superior photocatalytic activity, and robust chemical stability. Nonetheless, the efficacy of solar energy conversion is hampered by TiO2's wide bandgap and the swift recombination of photogenerated carriers. In pursuit of enhancing TiO2's photocatalytic prowess, a panoply of modification techniques has been explored over recent years. This work provides an extensive review of the strategies employed to augment TiO2's performance in photocatalytic hydrogen production, with a special emphasis on foreign dopant incorporation. Firstly, we delve into metal doping as a key tactic to boost TiO2's capacity for efficient hydrogen generation via water splitting. We elaborate on the premise that metal doping introduces discrete energy states within TiO2's bandgap, thereby elevating its visible light photocatalytic activity. Following that, we evaluate the role of metal nanoparticles in modifying TiO2, hailed as one of the most effective strategies. Metal nanoparticles, serving as both photosensitizers and co-catalysts, display a pronounced affinity for visible light absorption and enhance the segregation and conveyance of photogenerated charge carriers, leading to remarkable photocatalytic outcomes. Furthermore, we consolidate perspectives on the nonmetal doping of TiO2, which tailors the material to harness visible light more efficiently and bolsters the separation and transfer of photogenerated carriers. The incorporation of various anions is summarized for their potential to propel TiO2's photocatalytic capabilities. This review aspires to compile contemporary insights on ion-doped TiO2, propelling the efficacy of photocatalytic hydrogen evolution and anticipating forthcoming advancements. Our work aims to furnish an informative scaffold for crafting advanced TiO2-based photocatalysts tailored for water-splitting applications.