The transition from petrochemical-based resources to renewable biomass is a key objective in sustainable chemical production. Biomass-derived polyols are promising feedstocks for the production of light olefins, which are essential intermediates in the polymer and fuel industries. However, their selective deoxygenation remains challenging due to the hydrophilicity of polyols, the reliance of deoxydehydration (DODH) reactions on expensive rhenium-based catalysts, and the harsh reaction conditions typically required. Herein, a series of rhenium-based heterogeneous catalysts was prepared by supporting ReOx species on either single oxides (SiO2, Nb2O5, CeO2, ZrO2) or mixed metal oxides (SiO2-Nb2O5, CeO2-ZrO2) prepared via soft-template (ST) method. Extensive catalytic screening using diethyl tartrate as a model substrate revealed a strong dependence of the activity on the nature of the support. Among the investigated systems, the ReOx/SiO2-Nb2O5 catalyst emerged as the most active and robust system, delivering high yields under significantly milder conditions (130–170 °C), compared to typical DODH protocols. A combined experimental and computational analysis demonstrated that catalytic activity is governed by the interplay between support properties and the oxidation states distribution of surface rhenium species. In particular, a high fraction of reduced Re species in combination with high surface area correlate with enhanced activity, thus being identified as key requirements for optimal performance. The SiO2-Nb2O5 support enables efficient stabilization of active species and mitigates rhenium leaching, resulting in excellent recyclability over multiple catalytic cycles. These findings underscore the critical role of support composition and synthesis methodology in tuning catalytic performance. Overall, this work delivers a practical and scalable DODH protocol, offering a valuable step forward in the catalytic conversion of renewable feedstocks into high-value chemicals within a circular economy framework.

The authors regret the correction of the Acknowledgments. The abbreviation of the Institution is added (MICIU instead of MICIN). The authors would like to apologise for any inconvenience caused.

Co-Cu/SBA-15 systems have been studied for the reverse water gas shift (rWGS) reaction within mild temperature range of 250-650 degrees C. CuOx and CoOx species at different weight ratios were deposited from wet impregnation method over SBA-15 support. We have stated that pre-reduction treatment before reaction leads to the complete Co and Cu reduction for Co-Cu/SBA systems. A low copper content on Co/SBA system leads to similar CO2 conversion than monometallic Co-catalyst. However, competitive Sabatier side reaction appears almost suppressed. So, upon Cu incorporation a significant improvement on CO yield has been attained with respect to Co/SBA catalyst. Thus, a good compromise is attained at 450 degrees C using Co5Cu5/SBA catalyst for which a stable CO2 conversion of 22 % and 97 % CO selectivity has been obtained under lowest H2:CO2 ratio.

The main goal of the present study was to explore photocatalytic performance of the TiO2 -CuO mixture, for solar to hydrogen conversion at pilot plant scale under two different irradiation conditions (sunny and partly cloudy), focusing on high-temperature pretreat-ment of the catalyst mixture to try to improve TiO2 doping with copper. P25-TiO2 and commercial CuO were used with different amounts of Cu (2 wt% or 7 wt% Cu) calcined at 200-400 degrees C during several hours. Catalysts were tested at pilot plant scale using solar compound parabolic collectors, with glycerol as the sacrificial agent. The photocatalyst prepared after heating at 200 degrees C for 3 h and with 7 wt% Cu, resulted in higher hydrogen production than under the other heating conditions, and results were slightly better (5 -10%) than the reference values with the untreated catalysts. Photocatalytic efficiency was slightly lower at the higher calcination temperature (400 degrees C). CO2 production and formation of formate and glycolate clearly demonstrated glycerol photoreforming. The Cu from the calcined catalyst remaining on the solid was significantly less (2.5%) than on the non -calcined catalyst (4.2%), with an important fraction of lixiviated copper and copper deposition on the reactor walls. This is a critical drawback that must be considered for large-scale applications.(c) 2023 The Author(s). Published by Elsevier Ltd on behalf of Hydrogen Energy Publications LLC. This is an open access article under the CC BY-NC-ND license (http:// creativecommons.org/licenses/by-nc-nd/4.0/).

Surface defects engineered nano-Cu/TiO2 photocatalysts are synthesized through an easy and cost-effective microwave-assisted hydrothermal synthesis, mixing commercial P25 titania (TiO2) and oxalic acid (Ox), followed by 2.0 wt% Cu co-catalyst (labeled as Cu-2.0) loading through in situ photodeposition during reaction. The hydrothermal treatment does not affect the catalyst crystalline structure, morphology, nor the surface area. However, depending on the Ox/TiO2 molar ratio used an influence on the optical properties and on the reactivity of the system is detected. The presence of surface defects leads to intraband states formation between valence band and conduction band of bare titania, inducing an important enhancement in the photoactivity. Thus, Cu-2.0/gOx/P25 200 (where g is the weight of Ox and 200 the temperature in Celsius degrees used during the synthesis) have been successfully tested as efficient photocatalysts for hydrogen production through methanol (MeOH) reforming under UV light in a MeOH/ H2O solution (10% v/v) by fluxing the system with N-2, showing an increased reactivity compared to the bare Cu-2.0/P25 system.

Glycerol is a by-product in biodiesel production (in the range of g·L−1), so its photoreforming by photocatalysis is a way of valorising it. TiO2 in photocatalysis has been widely studied, although its efficiency is limited by the high energy band gap, and the electron-hole recombination. Its combination with different semiconductors should improve charge separation, extending also the absorption from UV to visible light. Cu and Ni oxides are two of the most efficient low-cost transition metal oxide catalysts. Experiments were carried out in a 25 L pilot plant connected to a compound parabolic solar collector. Different combinations of the three semiconductors, based on the concentration of each metal on TiO2 (Me, 5%, 7.2% and 10%) were evaluated. Evonik P25-TiO2, CuO and NiO were combined by mechanical mixing. Hydrogen was quantified by a micro gas chromatograph, and copper and nickel leaching by ICP-MS. The best hydrogen production (0.060 mMol kJ−1) was attained with a proportion of 10:1 of TiO2:MeO, that corresponds to a total metal concentration of 7.2 wt%, being Cu and Ni in the same proportion. Metal content in solution increased as the reaction progressed, but Ni lixiviation of <0.012 mg L−1 was not significant. Significant Cu leaching (>1 mg L−1) was observed. This article presents novel results, in a solar pilot plant, for determining which ternary mixture can give better results, as well as metal leaching into water. Handling relevant volume of water in anoxic conditions can help to understand the application of this technology for the production of hydrogen.

CuOx/LaCoO3 systems have been studied for the rWGS reaction under thermal assisted photocatalytic conditions within low temperature range of 180-330 degrees C. CuOx species deposited from chemical reduction method over LaCoO3 homogeneously covered the perovskite surface. The reduction pretreatment before reaction leads to the partial Co reduction and the complete reduction of Cu. A significant improvement on CO production has been attained upon Cu incorporation. In addition, upon UV-vis irradiation the CO production is also enhanced. Best results have been obtained for 5 wt% Cu. The highest synergistic effect was observed for the lowest temperature, for which catalytic contribution is negligible. Thus, a good compromise is attained at 300 degrees C for which a CO production of 5.45 mmol/h center dot g and 92 % selectivity, showing a good synergistic effect between thermo and thermo-photocatalytic activity.

Cobalt supported TiO2 catalysts have been prepared by wet-impregnation and by immobilization over APTES (3-aminopropyl triethoxysilane) grafted TiO2. Impregnated system showed better catalytic performance after reduction at 260 degrees C but significant deactivation is observed. On the contrary, functionalized catalyst showed better catalytic performance after reduction at 400 degrees C with notable stability. We have stated from CO-DRIFT operando analysis that impregnated system is strongly affected by negative SMSI (strong metal-support inter-action) upon reduction at higher temperature. While immobilization on APTES hinders the loss of metal active sites. The study of spent catalysts denotes that Co is redispersed in the impregnated catalyst while functionalized trends to form agglomerates.

Cu/TiO2/SrTiO3 hybrid structures have been synthesized by the simple impregnation method from Cu/TiO2 and SrTiO3 systems. The structural and surface characterization stated that Cu/TiO2/SrTiO3 composites form an effective covering of SrTiO3 by Cu/TiO2. The heterostructured catalysts lead to an outstanding improved photoactivity for hydrogen production from methanol photoreforming that would be related with the efficient separation of charge pairs favored by the Cu/TiO2/SrTiO3 heterojunction. The best photoproduction is attained for the 30 wt % SrTiO3 heterojunction showing 81.7 mmol/g H2 after 6 h (leading to an apparent quantum yield of ca 1%), 1.7 times higher than that of bare Cu/TiO2.

Cobalt supported on mesostructured TiO2 catalysts has been prepared by a wet-impregnation method. The Co/TiO2 catalytic system showed better catalytic performance after support calcination at 380 °C. Co nanoparticles appeared well distributed along the mesopore channels of TiO2. After reduction pretreatment and reaction, a drastic structural change leads to mesopore structure collapse and the dispersion of the Co nanoparticles on the external surface. Along this complex process, Co species first form discrete nanoparticles inside the pore and then diffuse out as the pore collapses. Through this confinement, a strong metal-support interaction effect is hindered, and highly stable metal active sites lead to better performance for Fischer-Tropsch synthesis reaction toward C5+ products.

This chapter overviews the state-of-the-art and recent advances in solar photocatalysis water splitting for hydrogen production. Several approaches are described to overcome the main strong handicap, as recombination of photogenerated pairs, fast competitive backward reactions, and the failure to absorb visible light photons. Photoreforming advantages for the overall water splitting reaction are discussed, as it is evident that these combined processes represent an environmentally friendly, cost-effective method for industrial byproducts or wastewater treatment. Factors affecting performance, that is, the structure and morphology of the catalyst in the reactor, light intensity, temperature, pH, and chemical nature of the sacrificial agent, are also described. The limited number of studies done on pilot-scale and the design of pilot-plant scale photoreactors for this purpose are discussed, including advances in photoreactors based on slurry and immobilized catalyst. Essential environmental assessment of photoreforming, since the wastewater generated could potentially harm the environment and human health, is also informed.

To improve TiO2 for H2 generation, one strategy for the separation of photogenerated charges is the formation of heterostructures with other materials. In particular, NiO is a photocatalyst known for its good stability and low cost. However, no studies at pilot scale using solar energy have been described. Consequently, an evaluation of a physical NiO:TiO2 mixture at pilot scale (25 L) with natural irradiation (2.10 m2 of sun-exposed surface) and with simultaneous glycerol photoreforming was explored. NiO:TiO2 50 mg & sdot;L- 1 resulted in the highest hydrogen production, showing an STH = 1.44%, considering only the UV fraction of the solar irradiation. H2 and CO2 production were analysed by on-line GC; Glycerol, dissolved organic carbon, carboxylic acids and nickel leaching were also evaluated. The NiO:TiO2 mixtures rendered a systematically lower H2 production in natural water than in high-purity water. The increase of ionic strength increased the mean size of particle clusters, promoting rapid sedimentation. All this indicates the importance of testing under real field conditions for attaining reliable solar to hydrogen (STH) efficiency.

The main goal of the present study was to explore pilot-scale combination of H-2 generation with simultaneous water disinfection or decontamination. Performance of a TiO2-CuO mixture for solar-to-hydrogen (STH) con-version was studied, focusing on treatment optimization (catalyst dose, proportion of semiconductors in the mixture and concentration of the sacrificial agent). Experiments were performed in a 25-L compound parabolic collector (2 m(2)) solar pilot plant specifically designed for photocatalytic hydrogen generation. The best operating conditions were 100 mg L-1 TiO2-CuO (10:1) with 0.075 M glycerol as the sacrificial agent. The best STH conversion attained was 0.9%. 25 mg L-1 imidacloprid was completely degraded (over 99%). The synergetic effect of anoxic conditions, TiO2:CuO and solar radiation caused a significant reduction (> 5 Log) in concen-tration of E. coli, used as a model waterborne pathogen, in less than 10 min.

The TiO2/WO3 photocatalysts were prepared by a simple assisted sonochemical -microwave combination. The wide surface and structural characterization of synthesized material confirmed that the adopted preparation method resulted in nanoparticulated crystallite anatase phase of TiO2 with a large surface area (> 200 m(2)/g), and the dispersion of WO3 on the surface of TiO2. The photoactivity was assessed for the photodegradation of ciprofloxacin (CIP) and oxytetracycline (OTC) antibiotics under UV and sunlight irradiation. The mineralization rate, toxicity assessment, pollutant concentration effect on photodegradation efficiency, and reusability potential under sunlight were all investigated. Results showed that TiO2 doped with 5 wt% of WO3 exhibited the best photocatalytic activity under UV (100% degradation) and solar light. Rate constants for CIP and OTC degradation showed that TiO2/WO3 significantly improved with respect to bare TiO2. The antibacterial study revealed that the photodegraded solutions became less toxic than the initial CIP and OTC solutions showing a significant decrease in the inhibition zone diameter and mineralization rates. The prepared TiO2/WO3 maintained high performances in the presence of high concentrations of pollutants as well as good stability after four consecutive uses. The increased photocatalytic activity is attributed to the incorporation of WO3, which extends the light absorption range and decreases the rate of electron -hole recombination.

Reduction pre-treatment at different temperatures were performed over Mo/HZSM-5 system before methane dehydroaromatiztion reaction. We have shown the crucial effect of reduction temperature on the final catalytic performance. Outstanding improvement in the aromatics conversion has been attained. Thus, H-2 formation form methane cracking reaction seems to be hindered for pre-treated catalysts. As a consequence, the deposition of coke in these samples appeared also notably suppressed. The optimum performance has been achieved for reduction pre-treatment at 550 degrees C. For this temperature, we have observed that the fraction of reduced Mo species is higher.

In this study, the promoting effect of rhenium addition as a co-dopant on Mo/ZSM-5 catalysts system has been analysed. Hence, bimetallic (Re-Mo/ZSM-5) catalysts have been synthesized using a sequential impregnation methodology. The catalytic performance for direct aromatization of methane reaction has been determined and correlated with their physical and chemical state combining multiple characterization techniques. An important synergy between Mo and Re, affected by the sequential impregnation, has been observed. Thus, Re1-Mo4/ZSM-5 in which Re has been incorporated first shows notably higher aromatic yields and stability against deactivation. Characterization results suggest that catalytic enhancement is due to the important effect of Re presence in close interaction with Mo. Improved evolution of ethane through C-C coupling would be correlated to this catalytic performance. As we discuss, Mo nature and location in the bimetallic systems are strongly conditioned by Re and the impregnation sequence and favours such intermediate step.

Optimization of Pt-promoted TiO2-based is key to promote the photocatalytic production of hydrogen using sacrificial alcohol molecules. Combination of doping and surface decoration of the mentioned base photoactive material is here exploited to maximize hydrogen yield. Using the quantum efficiency parameter, it is shown that the resulting composite system can boost activity up to 7.3 times within the whole methanol:water mixture ratio, yielding quantum efficiencies in the ca. 13-16 % range. The key role of the different components in generating charge carrier species and their use to trigger the sacrificial molecule evolution and control reaction kinetics are examined through an in-situ spectroscopic study. The study unveils the complex reaction mechanism, with generation of C1 to C3 molecules from different carbon-containing radicals, and interprets the physical origin of the huge H2 production enhancement occurring in doped-composite titania-based catalysts.

We have optimized the H-2 production by methanol thermo-photocatalytic reforming in the gas phase using Cu/TiO2 catalyst by tuning metal loading. Metal co-catalyst has been deposited by means of chemical reduction deposition. We have stated that thermo- and thermo-photocatalytic process leads to a notable H-2 production at 200 C. By in-situ FTIR studies we evidenced that formate formation follows a different evolution depending on the reforming experiment. These surface formate would lead to CO formation through dehydration reaction. At higher Cu content the low CO selectivity denote that water-gas-shift reaction would predominate and exalt H-2 yield. Thus, different optimum Cu content is found for each reforming experiment. While for the photocatalytic reforming Cu/TiO2 (2 wt%) is the best catalyst of the series, we should increase the Cu content to Cu/TiO2 (5 wt%) to achieve the optimum performance for thermo-photocatalytic reforming of methanol.

The influence of the reaction pathway of the sacrificial molecule oxidation to generate hydrogen is here investigated for lean and rich methanol reaction mixtures. Pt-TiO2 powders promoted or not with tin sulfide were used as catalysts. With the help of in situ infrared experiments under reaction conditions, methanol evolution was shown to take place by hole-related oxidation steps, with alkoxy and carbon-centered species as key radical species. The study analyzed quantitatively the fate and chemical use of the photons absorbed by the solids with the help of the quantum efficiency and the useful fraction of photons observables. Within this framework, the role of the sulfide component to promote photoactivity is interpreted, braiding chemical and photonic information.