A5090149461- Polyoxometalates: Synthesis and Applications
- Electrocatalysts for Energy Conversion
- Advanced Photocatalysis Techniques
- Advanced Nanomaterials in Catalysis
- Metal-Organic Frameworks: Synthesis and Applications
- Crystallization and Solubility Studies
- Oxidative Organic Chemistry Reactions
- X-ray Diffraction in Crystallography
- Radical Photochemical Reactions
- Chemical Synthesis and Reactions
- CO2 Reduction Techniques and Catalysts
- Porphyrin and Phthalocyanine Chemistry
- Electrochemical Analysis and Applications
- Advanced battery technologies research
- Sulfur-Based Synthesis Techniques
- Carbon dioxide utilization in catalysis
- Catalytic C–H Functionalization Methods
- Metal-Catalyzed Oxygenation Mechanisms
- N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
- Vanadium and Halogenation Chemistry
- Copper-based nanomaterials and applications
- Catalytic Processes in Materials Science
- Nanomaterials for catalytic reactions
- Ammonia Synthesis and Nitrogen Reduction
- TiO2 Photocatalysis and Solar Cells
University of Padua
2016-2025
Institute on Membrane Technology
2011-2018
University of Ferrara
2015-2018
Membrane Technology & Research (United States)
2018
University of Trieste
2012
Osnabrück University
2010
Institut Català d'Investigació Química
2009
Universitat Rovira i Virgili
2009
Princeton University
2008
University of Rome Tor Vergata
2007
Solid state and solution evidence confirms the embedding of an adamantane-like, Ru4O6 fragment by divacant, gamma-decatungstosilicate ligand. The resulting complex catalyzes water oxidation to oxygen with TON up 500 TOF > 450 h-1.
Abstract The functional core of oxygenic photosynthesis is in charge catalytic water oxidation by a multi‐redox Mn III /Mn IV manifold that evolves through five electronic states (S i , where =0–4). synthetic model system this cycle and its S 0 →S 4 intermediates the expected turning point for artificial photosynthesis. tetramanganese‐substituted tungstosilicate [Mn 3 O (CH COO) (A‐α‐SiW 9 34 )] 6− (Mn POM) offers an unprecedented mimicry natural reduced state; it features hybrid...
Photocatalysis has become a prominent tool in the arsenal of organic chemists to develop and (re)imagine transformations. However, only handful versatile photocatalysts (PCs) are available, hampering discovery new reactivities. Here, we report design complete physicochemical characterization 9-aryl dihydroacridines (9ADA) 12-aryl dihydrobenzoacridines (12ADBA) as strong reducing PCs. Punctual structural variations modulate their molecular orbital distributions unlock locally or...
Isostructural cubane-shaped catalysts [Co(III)(4)(μ-O)(4)(μ-CH(3)COO)(4)(p-NC(5)H(4)X)(4)], 1-X (X = H, Me, t-Bu, OMe, Br, COOMe, CN), enable water oxidation under dark and illuminated conditions, where the primary step of photoinduced electron transfer obeys to Hammett linear free energy relationship behavior. Ligand design catalyst optimization are instrumental for sustained O(2) productivity with quantum efficiency up 80% at λ > 400 nm, thus opening a new perspective in vitro molecular...
Converging UV−vis, EPR, rRaman, and DFT calculations highlight the evolution of [Ru4(H2O)4(μ-O)4(μ−OH)2(γ-SiW10O36)2]10−, 1, to high-valent intermediates. In analogy with natural enzyme, five different oxidation states, generated from have been found power catalytic cycle for water oxidation. A high electrophilic tetraruthenium(V)-hydroxo species is envisaged as competent intermediate, undergoing nucleophilic attack by an external molecule a key step in formation new O−O bond under conditions.
The tetraruthenium polyoxometalate water oxidation catalyst 1 performs very fast hole scavenging from photogenerated Ru(iii) polypyridine complexes, both in homogeneous solution and at a sensitized nanocrystalline TiO(2) surface.
The combined use of a tetranuclear Ru(II) dendrimeric photosensitizer (1) and tretraruthenium substituted polyoxotungstate (2) as the catalyst enables photo-induced water oxidation at 550 nm producing O(2) with an outstanding quantum yield 0.30.
Efficient photocatalytic conversion of carbon dioxide into valuable reduction products is a priority goal for artificial photosynthesis. Iridium(III) photocatalysts with combined 2-phenylpyridine (ppy) and 2,2′:6′,2″-terpyridine (tpy) ligand set have been shown to selectively reduce CO2 CO. Here, terpyridine modifications investigated that yield turnover number (TON) up 265, quantum 0.10, photocatalyst lifespan over 10 days. The key success the effect adding aromatic substituents tpy...
Aminocatalysis is a well-established tool that enables the production of enantioenriched compounds under mild conditions. Its versatility underscored by its seamless integration with various synthetic approaches. While combination aminocatalysis metal catalysis, photochemistry, and stoichiometric oxidants has been extensively explored, synergy electrochemical activation remains largely unexplored. Herein, we present successful merger electrochemistry to perform SOMO-type transformations,...
Direct photochemical conversion of CO2 into a single carbon‐based product currently represents one the major issues in catalysis reduction reaction (CO2RR). In this work, we demonstrate that combination an organic photosensitizer with heptacoordinated iron(II) complex allows to attain noble‐metal‐free system capable efficient and selective CO upon light irradiation presence N,N‐diisopropylethylamine (DIPEA) 2,2,2‐trifluoroethanol (TFE) as electron proton donor, respectively, unprecedented...
Graphical Abstract Twisted fibers with a helical structure are formed by self-assembly of chiral polyoxomolybdates (POMs) [(R*PO3)2Mo5O15]2− (R=CH3CH(NH3), CH3CH(CH3)CH(NH3)) through H-bonding. High-resolution TEM images single show an ordered substructure parallel rows about 2 nm in width, agreement the packing H-bonded POM subunits X-ray (see inset).
[structure: see text] Organic-inorganic hybrids synthesized from lacunary polyoxotungstates (POMs) have been screened as oxidation catalysts with H2O2 under MW irradiation. Yields up to 99% obtained in 25-50 min depending both on the POM structure and organic moiety. The reaction scope, optimized best performing catalyst [gamma-SiW10O36(PhPO)2]4-, includes epoxidation of terminal internal double bonds, alcohol oxidation, sulfoxidation, well oxygen transfer electron-deficient substrates...
Photoinduced water oxidation to molecular oxygen takes place in systems made of [Ru(bpy)3]2+ (bpy = 2,2′-bipyridine) as the photosensitizer, [Co4O4(O2CMe)4(py)4] (py pyridine) catalyst and Na2S2O8 sacrificial electron acceptor. The photochemical quantum yield process reaches outstanding value 30% depends on pH concentration. Transient absorption spectroscopy experiments aimed clarify first events photocatalytic are also reported.
Water oxidation is the crucial stage in chemical and molecular sequence of photosynthesis, designed by Nature to convert solar light into energy. The artificial "off-leaf" transposition a major goal energy research, aiming at continuous production hydrogen as fuel, through photo-catalytic splitting water. Success this task primarily depends on interplay light-activated multi-electron reduction cycles invention stable robust water catalysts, liberating oxygen with fast rates, high quantum...
The tetraruthenium polyoxometalate [Ru4(μ-O)4(μ-OH)2(H2O)4(γ-SiW10O36)2]10- (1) behaves as a very efficient water oxidation catalyst in photocatalytic cycles using Ru(bpy)32+ sensitizer and persulfate sacrificial oxidant. Two interrelated issues relevant to this behavior have been examined detail: (i) the effects of ion pairing between polyanionic cationic sensitizer, (ii) kinetics hole transfer from oxidized catalyst. Complementary charge interactions aqueous solution leads an static...
The artificial leaf project calls for new materials enabling multielectron catalysis with minimal overpotential, high turnover frequency, and long-term stability. Is graphene a better material than carbon nanotubes to enhance water oxidation energy applications? Here we show that functionalized tailored distribution of polycationic, quaternized, ammonium pendants provides an sp(2) nanoplatform anchor totally inorganic tetraruthenate catalyst, mimicking the oxygen evolving center natural...
Water oxidation catalysts: evolution of [Co4(H2O)2(α-PW9O34)2]10− to catalytically active species is assessed by laser flash photolysis in sacrificial photocatalytic cycles with Ru(bpy)32+ as a photosensitizer.
A salophen cobalt(II) complex enables water oxidation at neutral pH in photoactivated sacrificial cycles under visible light, thus confirming the high appeal of earth abundant single site catalysis for artificial photosynthesis.
Solar-to-fuel energy conversion relies on the invention of efficient catalysts enabling water oxidation through low-energy pathways. Our aerobic life is based this strategy, mastered by natural Photosystem II enzyme, using a tetranuclear Mn-oxo complex as oxygen evolving center. Within artificial devices, can be oxidized efficiently tailored metal-oxide surfaces such RuO2. The quest for catalyst optimization in vitro plagued elusive description active sites bulk oxides. Although molecular...
Abstract Oxygen evolution reaction (OER) is the most critical step in water splitting, still limiting development of efficient alkaline electrolyzers. Here we investigate OER activity Au–Fe nanoalloys obtained by laser‐ablation synthesis solution. This method allows a high amount iron (up to 11 at %) be incorporated into gold lattice, which not possible alloys synthesized other routes, due thermodynamic constraints. The Au 0.89 Fe 0.11 exhibit strongly enhanced comparison individual pure...
Twelve naphthochromenone photocatalysts (PCs) were synthesized on gram scale. They absorb across the UV/Vis range and feature an extremely wide redox window (up to 3.22 eV) that is accessible using simple visible light irradiation sources (CFL or LED). Their excited-state potentials, PC*/PC.- 1.65 V) PC.+ /PC* -1.77 V vs. SCE), are such these novel PCs can engage in both oxidative reductive quenching mechanisms with strong thermodynamic requirements. The potential of bimodal was benchmarked...