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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 Cu2.0) 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, Cu2.0/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 N2, showing an increased reactivity compared to the bare Cu2.0/P25 system., Validerad;2024;Nivå 2;2024-04-03 (joosat);Funder: MUR (CUP D43C22003090001, ECS00000043 – CUP N. H43C22000540006); Ministerio de Ciencia e Innovación (PLEC202‐007906, TED2021‐130173B‐C43); EU FEDER; Junta de Andalucía (P20‐00156); EUROFEL-ROADMAP ESFRI, Italian Ministry of University and Research;Full text license: CC BY-NC-ND

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 Cu2.0) 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, Cu2.0/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 N2, showing an increased reactivity compared to the bare Cu2.0/P25 system.

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.

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 °C but significant deactivation is observed. On the contrary, functionalized catalyst showed better catalytic performance after reduction at 400 °C with notable stability. We have stated from CO-DRIFT operando analysis that impregnated system is strongly affected by negative SMSI (strong metal-support interaction) 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.

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·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.

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 Cu2.0) 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, Cu2.0/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 N2, showing an increased reactivity compared to the bare Cu2.0/P25 system.

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, H2 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 ºC. For this temperature, we have observed that the fraction of reduced Mo species is higher.

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.

We report on a novel synthesis method, which produces NaY(MoO4)2 nanoparticles having an almost spherical shape and hydrophilic character. The procedure is also suitable for the preparation of NaY (MoO4)2-based nanophosphors by doping this host with lanthanide cations (Eu3+, Tb3+ and Dy3+), which, under UV illumination, exhibit intense luminescence whose color is determined by the selected doping cation (red for Eu3+, green for Tb3+ and yellow for Dy3+). The effects of the cations doping level on the luminescent properties are analyzed in terms of emission intensities and luminescent lifetime, to find the optimum phosphors. Finally, the performance of these nanophosphors and that of the undoped system for the photocatalytic degradation of rhodamine B, used as a model compound, is also analyzed

A series of gold-palladium catalysts supported in a mesoporous surface functionalized silica SBA-15 was studied for H2O2 direct synthesis. Support functionalization was performed using different organic groups (namely SO3H, NH2 and SH) while metal was then supported by an ion exchanged method. Different Au-Pd/SBA-15 catalysts were tested in the Direct Synthesis of Hydrogen Peroxide (DSHP). Organic functional groups (SH, SO3H and NH2) with acid-base properties acted as anchoring sites controlling both the dispersion of the metallic active phase and the chemical state of gold and palladium species as Au+ and Pd2+, respectively. Compared to a Au-Pd/SBA-15 system prepared by incipient wetness impregnation over non-functionalized SBA-15, catalytic performance is improved upon functionalization, increasing hydrogen peroxide rate in sulfonic-SBA-15 systems and reducing the hydrogenation/decomposition activity by adding amine groups. The occurrence of amine groups clearly suppresses the support microporosity and probably condition the metal cluster size. The analysis of particle size by TEM showed that sulfonated samples lead to a Pd size compromise which improves the H2O2 production hindering the competitive side reactions, particularly suppressed by the presence of amine groups.

A Cu/TiO2 photocatalyst has been synthesised by reducing a Cu precursor with NaBH4 onto the surface of a sulphate pretreated TiO2 obtained by a sol-gel procedure. The catalyst, that shows a clearly defined anatase phase with high crystallinity and relatively high surface area, and contains Cu2O and CuO deposits on its surface, has been used to produce hydrogen in a solar driven pilot plant scale photocatalytic reactor. Different electron donor aqueous solutions (methanol, glycerol, and a real municipal wastewater treatment plant influent) have been tested showing similar or even higher energy efficiency than those obtained using more expensive noble metal based photocatalytic systems. The glycerol solutions have provided the best reactive environments for hydrogen generation.

Understanding how a photocatalyst modulates its oxidation state, size, and structure during a photocatalytic reaction under operando conditions is strongly limited by the mismatch between (catalyst) volume sampled by light and, to date, the physicochemical techniques and probes employed to study them. A synchrotron micro-beam X-ray absorption spectroscopy study together with the computational simulation and analysis (at the X-ray cell) of the light-matter interaction occurring in powdered TiO-based monometallic Cu, Ni and bimetallic CuNi catalysts for hydrogen production from renewables was carried out. The combined information unveils an unexpected key catalytic role involving the phase contact between the reduced and oxidized non-noble metal phases in all catalysts and, additionally, reveals the source of the synergistic Cu-Ni interaction in the bimetallic material. The experimental method is applicable to operando studies of a wide variety of photocatalytic materials.