Photocatalysis is a promising sustainable technology to remove organic pollution and convert solar energy into chemical energy. Titanium dioxide has drawn extensive attention in this field owing to its high activity under UV light, good chemical stability, large availability, low price and low toxicity. However, the poor quantum efficiency derived from fast electron/hole recombination, the limited utilization of sunlight, and a weak reducing ability still hinder its practical application. Among the modification strategies of TiO2 to enhance its performance, the construction of heterojunctions with other semiconductors is a powerful and versatile way to maximise the separation of photogenerated charge carriers and steer their transport toward enhanced efficiency and selectivity. Here, the research progress and current status of TiO2 modification are reviewed, focusing on heterojunctions. A rapid evolution of the understanding of the different charge transfer mechanisms is witnessed from traditional type II to the recently conceptualised S-scheme. Particular attention is paid to different synthetic approaches and interface engineering methods designed to improve and control the interfacial charge transfer, and several cases of TiO2 heterostructures with metal oxides, metal sulfides and carbon nitride are discussed. The application hotspots of TiO2-based photocatalysts are summarized, including hydrogen generation by water splitting, solar fuel production by CO2 conversion, and the degradation of organic water pollutants. Hints about less studied and emerging processes are also provided. Finally, the main issues and challenges related to the sustainability and scalability of photocatalytic technologies in view of their commercialization are highlighted, outlining future directions of development.

Prospective photocatalytic ammonia synthesis process has received more attentions but quite challenging with the low visible light utilization and weak N2 molecule absorption ability around the photocatalysts. Herein, interface reconstruction of MXene-Ti3C2/CeO2 composites with high-concentration active sites through the carbon-doped process are presented firstly, and obvious transition zones with the three-phase reaction interface are formed in the as-prepared catalysts. The optimal co-doped sample demonstrates an excellent photo response in the visible light region, the strongest chemisorption activity and the most active sites. Moreover, much more in-situ extra oxygen defects are also produced under light irradiation. It is expected that the double decorated catalyst shows a remarked ammonia production rate of above 0.76 mmol gcal-1·h-1 under visible-light illumination and a higher apparent quantum efficiency of 1.08 % at 420 nm, which is one of the most completive properties for the photocatalytic N2 fixation at present.

Cyclic amino(alkyl) and cyclic amino(aryl) carbenes (cAACs/cAArCs) have been established as very useful ligands for catalytic and photonic applications of transition metal complexes. Herein, we describe the synthesis of a structurally related sterically demanding, electrophilic [2.2]isoindolinophanyl-based carbene (iPC) with a [2.2]paracyclophane moiety. The latter leads to more delocalized frontier orbitals and intense green fluorescence of (HiPC)OTf (2) from an intra-ligand charge transfer (1ILCT) state in the solid state. Base-promoted synthesis of the free carbene led to an unusual ring expansion and subsequent dimerization reaction, but the beneficial ligand properties can be exploited by trapping in situ at a metal center. The iPC ligand is a very potent π-chromophore, which participates in low energy metal-to-ligand (ML)CT transitions in [RhCl(CO)2(iPC)] (4) and IL-\"through-space\"-CT transitions in [Au(iPC)2]OTf (5). The steric demand of the iPC leads to high stability of 5 against air, moisture, or solvent attack, and ultralong-lived green phosphorescence with a lifetime of 185 μs is observed in solution. The beneficial photophysical and electronic properties of the iPC ligand, including a large accessible π surface area, were exploited by employing highly efficient energy transfer (EnT) photocatalysis in a [2+2] styrene cycloaddition reaction using 5, which outperformed other established photocatalysts in comparison.

In this study, a co-catalytic route was explored to enhance the photo-ozone catalytic degradation of volatile organic compounds (VOCs). NiCo2O4 was loaded onto the surface of CeO2 nanoparticles to create a composite catalyst (10%NiCo2O4/CeO2). The integration of NiCo2O4 onto CeO2 enhanced the interaction between the catalyst and toluene, a representative VOC, resulting in significantly increased toluene adsorption without a corresponding increase in specific surface area. This integration also improved the utilization of charge carriers and conversion of ozone to O2-. Under visible light irradiation, H2O accumulated charge carriers at 10%NiCo2O4/CeO2\'s surface, facilitating both ozone utilization and toluene adsorption. Another benefit of NiCo2O4 loading was its ability to enhance the conversion efficiency of solar energy. Consequently, the toluene removal and mineralization efficiencies of 10%NiCo2O4/CeO2 were enhanced by 182% and 309% compared to CeO2, and by 201% and 357% compared to NiCo2O4, respectively. Overall, this study demonstrated a novel co-catalyst design strategy for enhancing the photo-ozone catalytic degradation of VOCs.

Piezo-photocatalysis combines photocatalysis and piezoelectric effects to enhance catalytic efficiency by creating an internal electric field in the photocatalyst, improving carrier separation and overall performance. This study presents a high-performance piezo-photocatalyst for efficient dye degradation using a synergistic barium titanate (BTO)-MXene composite. The composite was synthesized via a facile method, combining the unique properties of BTO nanoparticles with the high conductivity of MXene. The structural and morphological analysis confirmed the successful formation of the composite, with well-dispersed BTO nanoparticles on the MXene surface. The piezo-photocatalytic activity of the composite was evaluated using a typical dye solution (Rhodamine B: RhB) under ultraviolet irradiation and mechanical agitation. The results revealed a remarkable enhancement in dye degradation (90 % in 15 min for piezo-photocatalysis) compared to individual stimuli (58.2 % for photocatalysis and 95.8 % in 90 min for piezocatalysis), highlighting the synergistic effects between BTO and MXene. The enhanced catalytic performance was attributed to the efficient charge separation and transfer facilitated by the composite\'s structure, leading to increased reactive species generation and dye molecule degradation. Furthermore, the composite exhibited excellent stability and reusability, showcasing its potential for practical applications in wastewater treatment. Overall, this work represents a promising strategy for designing high-performance synergistic catalysts, addressing the pressing need for sustainable solutions in environmental remediation.

Efficient photocatalytic solar CO2 reduction presents a challenge because visible-to-near-infrared (NIR) low-energy photons account for over 50% of solar energy. Consequently, they are unable to instigate the high-energy reaction necessary for dissociating C═O bonds in CO2. In this study, we present a novel methodology leveraging the often-underutilized photo-to-thermal (PTT) conversion. Our unique two-dimensional (2D) carbon layer-embedded Mo2C (Mo2C-Cx) MXene catalyst in black color showcases superior near-infrared (NIR) light absorption. This enables the efficient utilization of low-energy photons via the PTT conversion mechanism, thereby dramatically enhancing the rate of CO2 photoreduction. Under concentrated sunlight, the optimal Mo2C-C0.5 catalyst achieves CO2 reduction reaction rates of 12000-15000 μmol·g-1·h-1 to CO and 1000-3200 μmol·g-1·h-1 to CH4. Notably, the catalyst delivers solar-to-carbon fuel (STF) conversion efficiencies between 0.0108% to 0.0143% and the STFavg = 0.0123%, the highest recorded values under natural sunlight conditions. This innovative approach accentuates the exploitation of low-frequency, low-energy photons for the enhancement of photocatalytic CO2 reduction.

To solve environmental-related issues (wastewater remediation, energy conservation and air purification) caused by rapid urbanization and industrialization, synthesis of novel and modified nanostructured photocatalyst has received increasing attention in recent years. We herein report the facile synthesis of in situ nitrogen-doped chemically anchored TiO2 with graphene through sol-gel method. The structural analysis using X-ray diffraction showed that the crystalline nitrogen-doped graphene-titanium dioxide (N-GT) nanocomposite is mainly composed of anatase with minor brookite phase. Raman spectroscopy revealed the graphene characteristic band presence at low intensity level in addition to the main bands of anatase TiO2. X-ray photoelectron spectroscopy analysis disclosed the chemical bonding of TiO2 with graphene via Ti-O-C linkage, also the substitution of nitrogen dopant in both TiO2 lattice and into the skeleton of graphene nanoflakes. UV-Vis absorption spectroscopy analysis established that the modified material can efficiently absorb the longer wavelength range photons due to its narrowed band gap. The N0.06-GT material showed the highest degradation efficiency over methylene blue (MB, ∼98%) under UV and sulfamethoxazole (SMX, ∼ 90.0%) under visible light irradiation. The increased activity of the composite is credited to the synergistic effect of high surface area via greater adsorption capacity, narrowed band gap via increased photon absorption, and reduced e-/h+ recombination via good electron acceptability of graphene nanoflakes and defect sites (Ti3+ and oxygen vacancy (Vo)). The ROS experiments further depict that primarily hydroxyl radicals (OH•) and superoxide anions (O2•-) are responsible for the pollutant degradation in the process redox reactions. In summary, our findings specify new insight into the fabrication of this new material whose efficiency can be further tested in applications like H2 production, CO2 conversion to value-added products, and in energy conservation and storage.

The absorption of light by photosensitizers has been shown to offer novel reactive pathways through electronic excited state intermediates, complementing ground state mechanisms. Such strategies have been applied in both photocatalysis and photoredox catalysis, driven by generating reactive intermediates from their long-lived excited states. One developing area is photoinduced ligand-to-metal charge transfer (LMCT) catalysis, in which coordination of a ligand to a metal center and subsequent excitation with light results in the formation of a reactive radical and a reduced metal center. This mini review concerns the foundations and recent developments in ligand-to-metal charge transfer in transition metal catalysis focusing on the organic transformations made possible through this mechanism.

The development of effective photocatalysts for the reduction of Cr(VI) and the degradation of antibiotics remains a challenge. The present work reports the development of a novel heterojunction composite material, BiOCl/BaTiO3@Co-BDC-MOF (BOC/BTO@Co-MOF), based on solvothermal techniques. To characterize the surface and bulk features of the material, techniques such as FE-SEM, HR-TEM, BET/BJH, XPS, FT-IR, p-XRD, and UV-Vis-DRS were used. Based on the results, the BiOCl/BaTiO3 nanocomposites are uniformly dispersed on the rod-shaped Co-BDC MOF, resulting in a layered texture on the surface. A further advantage of the composite structure is the strong interfacial enhancement facilitating the separation of photoexcited electron-hole pairs. Also, compared to its pristine counterparts, the heterostructure material exhibited excellent surface area and pore properties. The photocatalytic efficiency towards reduction and degradation of Cr(VI)/SMX pollutants were evaluated by optimizing various analytical parameters, such as pH, catalytic loading concentrations, analyte concentration, and scavenger role. The specially designed BOC/BTO@Co-MOF composite achieved a 96.5% Cr(VI) reduction and 98.2% SMX degradation under 60.0-90.0 min of visible light illumination at pH 3.0. This material is highly reusable and has a six-time recycling potential. The findings of this study contribute to a better understanding of the efficient decontamination of inorganic and organic pollutants in water purification systems.

The widespread use of pharmaceutical pollutants seriously threatens the environment and human well-being. In the present study, zinc ferrite nanoparticles (ZnFe2O4 NPs) have been synthesized by co-precipitation method and used as photocatalyst for the degradation of two most commonly prescribed painkillers, piroxicam (PXM) and paracetamol (PCM), via heterogenous Fenton process under the solar light. The synthesized ZnFe2O4 NPs showed a narrower band gap i.e. 1.87 eV, signifying the ability to efficiently work in visible light range. In the context of photocatalytic applications, the operational conditions were optimized to achieve maximum degradation. PCM and PXM were completely degraded (100%) at the optimized photocatalytic dose (20 mg L-1), reaction time (180 minutes), initial drug concentration (10 mg L-1), and pH (6.0), which is close to the natural environment. The extent of mineralization as estimated by the reduction of TOC was observed to be ∼ 91 and 82% for PCM and PXM respectively. Kinetic studies revealed that photocatalytic degradation followed pseudo-first-order kinetics. Moreover, the ZnFe2O4 NPs retained ∼ 90 % of photocatalytic activity after five consecutive reaction cycles, showing high reusability and stability of catalyst.