Search Results (40)

Solar glycerol photoreforming was investigated on Au-Ni/CeO₂ photocatalysts with an overall metal content equal to 1wt% and different Au/Ni weight ratios. The deposition of gold over ceria was performed by two different methods, deposition–precipitation and photoreduction. Deposition–precipitation was the best method to deposit gold on CeO₂ with the formation of small Au nanoparticles (around 4 nm). The most active sample (0.9 wt% Au-0.1 Ni wt%/CeO₂) provided a H₂ production rate of 350 µmol/gcat∙h, much higher than the corresponding monometallic samples. A higher amount of Ni led to detrimental effects in H₂ production, likely due to the covering of the gold surface active sites by Ni. On the contrary, the presence of a small amount of Ni (0.1 wt%) allowed a remarkable improvement of the Au/CeO₂ photocatalytic stability after consecutive runs of simulated solar irradiation. This finding, as well as the activation of synergistic effects, the improved charge carrier separation, and the exploitation of the localized surface plasmon resonance property of gold, led to the proposal of an alternative photocatalytic system to the most investigated TiO₂-based photocatalysts for H₂ production. The enhanced stability is promising to further foster the investigation of these photocatalysts applied to sustainable H₂ production. Full article

The global plastic crisis, with over 400 million metric tons produced annually and minimal recycling, demands urgent solutions. Photocatalytic plastic photoreforming offers a dual benefit: converting non-recyclable plastics into hydrogen fuel and valuable chemicals using solar energy under mild conditions. This critical review highlights recent advances in photocatalyst design, including semiconductors, MOF-derived materials, and co-catalyst systems, and explores key insights into plastic degradation mechanisms and reactor configurations. Operational factors such as pH, light intensity, and flow dynamics are discussed for their impact on hydrogen yield and product selectivity. Life cycle and techno-economic assessments reveal current challenges in efficiency, scalability, and cost to illuminate the feasibility of implementing the technology at industrial scale. This study suggests that innovations in catalyst engineering, light management, and system integration provide viable paths forward. With its potential to upcycle plastic waste and contribute to low-carbon hydrogen economies, photoreforming represents a promising approach in advancing circular economy goals, especially when coupled with policy support and smart separation strategies. Full article

Photo-reforming waste polyethylene terephthalate (PET) in alkaline aqueous solutions is a novel approach for green hydrogen production. This study focuses on improving the catalytic efficiency of Pt/TiO₂ for the photo-reforming of waste PET using an innovative dark deposition method to deposit Pt single atoms on nano TiO₂ (Pt/TiO₂), thereby increasing the catalytic efficiency while reducing the cost of the catalyst. The precursor concentration was optimized to control the size and distribution of the Pt clusters/atoms, and the TiO₂ support was annealed at different temperatures to modify the properties of Pt/TiO₂. Nine Pt/TiO₂ catalysts were synthesized using different Pt precursor concentrations and annealing temperatures. The catalysts were characterized to measure their morphological, crystalline, and electronic properties, as well as their hydrogen yields via PET photo-reforming. The hydrogen conversion efficiency and external quantum yield (EQY) were calculated and compared with those of traditional direct-deposited catalysts. The correlation between the different characteristics of the dark-deposited and direct-deposited catalysts and their influence on the hydrogen yield in the photo-reforming process was statistically analyzed using principal component analysis. Catalysts deposited under dark conditions exhibited 5-fold and 7-fold enhancements in hydrogen conversion efficiency and EQY, respectively, compared to conventional catalytic systems. These findings indicate that the proposed catalytic system provides a viable solution for minimizing Pt loading, reducing the cost of the catalyst, and maintaining a higher hydrogen conversion efficiency. Full article

WO₃/Ag/TiO₂ composite photoelectrodes were formed via the high-temperature calcination of a WO₃ film, followed by the sputtering of a very thin silver film and deposition of an overlayer of commercial TiO₂ nanoparticles. These synthetic photoanodes were characterized in view of the oxidation of a model organic compound glucose combined with the generation of hydrogen at a platinum cathode. During prolonged photoelectrolysis under simulated solar light, these photoanodes demonstrated high and stable photocurrents of ca. 4 mA cm⁻² due, on one hand, to the occurrence of the so-called photocurrent doubling and, on the other hand, to the plasmonic effect of Ag nanoparticles. The post-photoelectrolysis analyses of the electrolyte demonstrated the formation of high-value final glucose photo-reforming products, principally gluconic acid, erythrose and formic acid. Full article

Biotemplating technique allows the synthesis of catalysts, recreating the sophisticated structure of nature templates. In this work, some biotemplated TiO₂ semiconductors were synthesized using Olea europaea leaves as templates. Then, g-C₃N₄ was coupled to materials to later incorporate Pt on the surface or as dopant in the structure to evaluate the efficiency of the solids in two photocatalytic applications to valorize biomass: hydrogen production through glycerol photoreforming, and photoacetalization of cinnamaldehyde with 1,2-propanediol. In glycerol photoreforming, the presence of Pt (superficial or dopant) enhanced hydrogen production, being Pt@AOLCN (a heterojunction containing biotemplated TiO₂, g-C₃N₄, and Pt) the system that exhibited the highest efficiency (3053.4 µmol·g_cat⁻¹·h⁻¹). For photoacetalization, while Pt reduced cinnamaldehyde conversion, it improved selectivity when incorporated on TiO₂. Notably, carbon nitride (CN) exhibited the highest yield after 16 h of testing. The study emphasizes the importance of tailoring catalyst selection to specific reactions, as efficiency is closely tied to the structural and chemical properties of the materials. These findings contribute to the development of efficient photocatalysts for sustainable biomass valorization processes. Full article

Pt-TiO₂ systems are the most widely used photocatalysts in the production of green hydrogen from glycerol photoreforming. To incorporate metals on the surface of materials, photodeposition is the most used method because it employs mild conditions. However, despite its use, there are some parameters that have not been deeply studied, such as the appropriate metal loading and the method itself, to obtain a better dispersion of Pt. In this work, six Pt-TiO₂ catalysts were synthesized by a classical photodeposition method employing UV radiation. The studied Pt wt.% range was 0.15–0.60 wt.%, being incorporated in one step or in subsequent ones. HRTEM analyses showed that both methods allowed a homogeneous distribution of Pt, and in both, the particle size was around 2.3–3.6 nm, increasing with metal loading. The photocatalytic activity of materials was tested in glycerol photoreforming under UV radiation, and the 0.45 wt.% Pt-containing solid that had been synthesized in one step was the one that allowed the highest hydrogen production. This might suggest that around 0.40% is the appropriate metal loading for hydrogen production under these conditions and that incorporating the desired metal percentage in one step is the most efficient method in terms of energy and time savings. Full article

The present work focuses on TiO₂ modification with carbon dots (CDs) using a hydrothermal process, which results in the synthesis of CD/TiO₂ nanocomposite photocatalysts characterized by exceptional optoelectronic properties. The structural and physicochemical properties of the obtained nanocomposites, which contained varying amounts of CDs, were precisely assessed. HR-TEM analysis showed that the prepared nanocomposites consisted of rod-shaped TiO₂ nanoparticles and CDs well-dispersed on their surface. The optical properties of the nanocomposites were studied using UV–vis diffuse reflectance spectroscopy. All CD/TiO₂ samples presented decreased energy gap values compared with bare TiO₂ samples; the band gap was further decreased as the CD concentration rose. Electrochemical measurements revealed that the presence of CDs improved the photocurrent response of the TiO₂, presumably due to enhanced charge separation and decreased recombination. The synthesized nanomaterials were used as photocatalysts to produce hydrogen via the photoreforming of ethanol and glycerol green organic compounds, under 1-sun illumination. The photocatalytic experiments confirmed that the optimum loading of CDs corresponded to a percentage of 3% (w/w). Ethanol photoreforming led to a H₂ production rate of 1.7 μmol∙min⁻¹, while in the case of the glycerol sacrificial agent, the corresponding rate was determined to be 1.1 μmol∙min⁻¹. The recyclability study revealed that the photocatalyst exhibited consistent stability during its reuse for hydrogen production in the presence of both ethanol and glycerol. Full article

The development of efficient and inexpensive photocatalysts for the production of high-value chemicals from the photoreforming of biomass is a highly attractive strategy to establish the production of chemicals from sustainable resources. In this work, Fe-loaded montmorillonite/TiO₂ composite (Fe-Mt/TiO₂), pure TiO₂, Mt/TiO₂ and Mt/Fe-TiO₂ were fabricated and further utilized as photocatalysts for the production of formic acid from glucose under visible-light irradiation. Among the as-prepared composites, the Fe-Mt/TiO₂ exhibited the highest glucose conversion (83%), formic acid production (44%) and formic acid selectivity (53%). The effective heterojunction between Fe-Mt and TiO₂ is proposed to describe the superior photocatalytic activity of Fe-Mt/TiO_2, which effectively suppressed the recombination of the photogenerated electrons and holes during the reaction. Mechanism investigations suggested that the selective photocatalytic oxidation of glucose into formic acid by Fe-Mt/TiO₂ mainly occurred through an α-scission reaction pathway, driven by the main active species as ^•O₂⁻ and ¹O₂. The research findings in this work suggested that the Fe-Mt/TiO₂ composite can be applied as a low-cost, easy-to-prepare, reusable and selective photocatalyst for sustainable synthesis of high-value chemicals from biomass-derived substrates. Full article

g-C₃N₄ has been regarded as a promising photocatalyst for photo-reforming antibiotics for H₂ production but still suffers from its high charge recombination, which has been proven to be solvable by constructing a g-C₃N₄ homo-junction. However, those reported methods based on uncontrollable calcination for preparing a g-C₃N₄ homo-junction are difficult to reproduce. Herein, an amorphous/crystalline g-C₃N₄ homo-junction (ACN/CCN) was successfully synthesized via the electrostatic self-assembly attachment of negatively charged crystalline g-C₃N₄ nanorods (CCN) on positively charged amorphous g-C₃N₄ sheets (ACN). All the ACN/CCN samples displayed much higher photo-reforming of antibiotics for H₂ production ability than that of pristine ACN and CCN. In particular, ACN/CCN-2 with the optimal ratio exhibited the best photocatalytic performance, with a H₂ evolution rate of 162.5 μmol·g⁻¹·h⁻¹ and simultaneous consecutive ciprofloxacin (CIP) degradation under light irradiation for 4 h. The UV–vis diffuse reflectance spectra (DRS), photoluminescence (PL), and electrochemical results revealed that a homo-junction is formed in ACN/CCN due to the difference in the band arrangement of ACN and CCN, which effectively suppressed the charge recombination and then led to those above significantly enhanced photocatalytic activity. Moreover, H₂ was generated from the water reduction reaction with a photogenerated electron (e⁻), and CIP was degraded via a photogenerated hole (h⁺). ACN/CCN exhibited adequate photostability and reusability for photocatalytic H₂ production with simultaneous CIP degradation. This work provides a new idea for rationally designing and preparing homo-junction photocatalysts to achieve the dual purpose of chemical energy production and environmental treatment. Full article

Pure Ce_0.5Zr_0.5O₂ and Au (0.1–1.0 wt.%)-deposited Ce_0.5Zr_0.5O₂ nanomaterials were synthesized via hydrothermal and non-aqueous precipitation methods using gold acetate as a chloride-free Au precursor. The synthesized nanostructures exhibited enhanced photocatalytic activity for hydrogen production via aqueous bioethanol photoreforming under visible light. Different characterization tools such as powder XRD, HRTEM, FT-IR, DR UV-vis, XPS and N₂ gas adsorption were used to analyze the physicochemical properties of the synthesized photocatalysts. The band gap value was lowered from 3.25 eV to 2.86 eV after Au nanoparticles were deposited on the surface of Ce_0.5Zr_0.5O₂. The 1.0 wt.% Au-deposited Ce_0.5Zr_0.5O₂ sample exhibited the highest photocatalytic activity for H₂ production (3210 μmol g⁻¹) due to its low band gap, the presence of more oxygen vacancies and its porous character. The EIS results reveal that the deposition of 1.0 wt.% Au nanoparticles is responsible for the highest charge separation efficiency with an increased lifetime of photogenerated e⁻/h⁺ species compared to the other samples. In addition, the presence of plasmonic Au is responsible for the effectiveness of the electron trap in improving the rate of H₂ formation. Full article

The photocatalytic reduction of CO₂ into solar fuel is considered a promising approach to solving the energy crisis and mitigating the environmental pollution caused by anthropogenic CO₂ emission. Some powder photocatalysts have been demonstrated as efficient, but their drifting properties, along with difficult separation (catalyst and product), make continuous mode reaction very challenging, particularly in the liquid phase. In order to make this process commercially viable and economically more efficient, we have developed a simple and scalable method for immobilizing TiO₂ P25 over the surface of glass slides using an organic-based surfactant. Improved adhesion properties and the homogeneous dispersion of catalyst nanoparticles were achieved. A holder was designed with 3D printing technology in such a way that it can hold up to six slides that can be dipped simultaneously into the suspension or solution of desired materials for a uniform and homogeneous deposition. The resulting surfaces of the dip-coated materials (e.g., TiO₂ P25) were further modified by adding metallic nanoparticles and thoroughly characterized via XRD, DRS UV–Vis, SEM, and SEM–EDX. Photocatalytic tests have been performed for two major applications, viz., hydrogen production via the photoreforming of glucose and the photoreduction of CO₂ into different solar fuels. The latter tests were performed in a specially designed, high-pressure reactor with Ag/P25 supported catalysts, which exhibited about three times higher formic acid productivity (ca. 20 mol/kg_cat h) compared to the dispersed catalyst, with enhanced stability and recoverability. It is to note that catalysts deposited on the glass slides can easily be recovered and the materials did not show any weight loss. To the best of our knowledge, the obtained formic acid productivity is highest among the published literature. Full article

Several biochars were synthesized from olive stones and used as supports for TiO₂, as an active semiconductor, and Pt as a co-catalyst (Pt/TiO₂-PyCF and Pt/TiO₂-AC). A third carbon-supported photocatalyst was prepared from commercial mesoporous carbon (Pt/TiO₂-MCF). Moreover, a Pt/TiO₂ solid based on Evonik P25 was used as a reference. The biochars used as supports transferred, to a large extent, their physical and chemical properties to the final photocatalysts. The synthesized catalysts were tested for hydrogen production from aqueous glycerol photoreforming. The results indicated that a mesoporous nature and small particle size of the photocatalyst lead to better H₂ production. The analysis of the operational reaction conditions revealed that the H₂ evolution rate was not proportional to the mass of the photocatalyst used, since, at high photocatalyst loading, the hydrogen production decreased because of the light scattering and reflection phenomena that caused a reduction in the light penetration depth. When expressed per gram of TiO₂, the activity of Pt/TiO₂-PyCF is almost 4-times higher than that of Pt/TiO₂ (1079 and 273 mmol H₂/g_TiO2, respectively), which points to the positive effect of an adequate dispersion of a TiO₂ phase on a carbonaceous support, forming a highly dispersed and homogeneously distributed titanium dioxide phase. Throughout a 12 h reaction period, the H₂ production rate progressively decreases, while the CO₂ production rate increases continuously. This behavior is compatible with an initial period when glycerol dehydrogenation to glyceraldehyde and/or dihydroxyacetone and hydrogen predominates, followed by a period in which comparatively slower C-C cleavage reactions begin to occur, thus generating both H₂ and CO₂. Full article

Photoreforming biomass-derived waste such as glycerol into hydrogen fuel is a renewable hydrogen generation technology that has the potential to become important due to unavoidable CO₂ production during methane steam reforming. Despite tremendous efforts, the challenge of developing highly active photocatalysts at a low cost still remains elusive. Here, we developed a novel photocatalyst with a hybrid support comprising reduced graphene oxide (rGO) and TiO₂ nanorods (TNR). rGO in the hybrid support not only performed as an excellent scavenger of electrons from the semiconductor conduction band due to its suitable electrochemical potential, but also acted as an electron transport highway to the metal co-catalyst, which otherwise is not possible by simply increasing metal loading due to the shadowing effect. A series of hybrid supports with different TNR and rGO ratios were prepared by the deposition method. Pd nanoparticles were deposited over hybrid support through the chemical reduction method. Pd/rGO-TNRs photocatalyst containing 4 wt.% rGO contents in the support and 1 wt.% nominal Pd loading demonstrated hydrogen production activity ~41 mmols h⁻¹g⁻¹, which is 4 and 40 times greater than benchmark Au/TiO₂ and pristine P25. The findings of this works provide a new strategy in optimizing charge extraction from TiO₂, which otherwise has remained impossible due to a fixed tradeoff between metal loading and the detrimental shadowing effect. Full article

Several studies have shown that combining TiO₂ and Cu₂O enhances the photocatalytic activity of the material by generating a heterojunction capable of extending the light absorption in the visible and reducing the electron-hole recombination rate. Ball milling has been chosen as an alternative methodology for photocatalyst preparation, among the several techniques documented in the literature review. The results of a previously reported investigation enabled the identification of the most effective photocatalyst that can be prepared for hydrogen generation by combining Cu₂O and TiO₂ (i.e., 1%wt. Cu₂O in TiO₂ photocatalyst prepared by ball-milling method at 200 rpm and 1 min milling time). To optimize photocatalytic hydrogen generation in the presence of the greatest photocatalyst, the effects of (i) sacrificial species and their concentration, (ii) temperature, and (iii) pH of the system are taken into account, resulting in a light-to-chemical energy efficiency of 8% under the best-tested conditions. Last but not least, the possibility of using the present photocatalytic system under direct solar light irradiation is evaluated: the results indicate that nearly 60% of the hydrogen production recorded under sunlight can be attributed to the visible component of the solar spectrum, while the remaining 40% can be attributed to the UV component. Full article

Hydrogen production is mainly based on the use of fossil fuels, but currently, many alternative routes are being developed, among which the photo-reforming of oxygenated organic compounds stands out. Recently, several studies have been carried out in order to develop new techniques to create bio-inspired TiO₂ structures. One of these is ‘biotemplating’, a process that replicates a biological system in an inorganic TiO₂-based structure. In this study, olive by-products—olive leaves—are valorized as a biotemplate for the synthesis of new Fe-TiO_2- and Cu-TiO₂-based photocatalysts with the aim of improving the replication of the leaf structure and enhancing hydrogen photoproduction. In conclusion, the incorporation of iron and copper decreases the band gap and increases the energetic disorder at the band edges. Moreover, it is verified by SEM and TEM that the metals are not found forming particles but are introduced into the formed TiO₂ structure. The accuracy of the internal and external structure replication is improved with the incorporation of Fe in the synthesis, while the incorporation of Cu substantially improves the production of hydrogen, which is multiplied 14 times under UV light and 6 times under sunlight, as compared to a pure TiO₂ structure. Full article