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Abstract: The potentiostatic anodization of metallic tungsten has been investigated in different solvent/electrolyte compositions with the aim of improving the photoelectrochemical performances of the tungsten oxide layer. Among the explored electrolytes, the anodization in the NMF/H2O/NH4F solvent mixture was found to produce the most efficient WO3 photoanodes, which, combining spectral sensitivity, high electrochemically active surface and improved charge transfer kinetics, outperform, under simulated solar illumination, most of the reported nanocrystalline substrates produced by anodization in aqueous electrolytes and by sol gel methods. While the preparation of the photoelectrodes is a slow process at room temperature (20°C), it could be greatly accelerated (x 10) by carrying out the anodization at 40-50°C, thus proving to be a fast and convenient approach to the production of high performing WO3 photoactive substrates directly connected to a metal electron collector. [Copyright &y& Elsevier]

Dye solar cells with Co(III)/Co(II) redox mediators have been prepared. To obtain higher conversion efficiencies, the recombination between photoinjected electrons and Co(III) species was minimized by deposition of a thin Al2O3 blocking layer over the mesoporous TiO2 surface. Measurements of current-voltage characteristic curves, both under illumination and in dark conditions, together with electrochemical impedance spectroscopy demonstrate the great effectiveness of the addition of a blocking layer in cells containing cobalt based electrolyte, by substantially reducing the recombination current. The consequent power conversion efficiency increase is more than double, passing from 0.94% to 2.48% under 300 W m-2 AM 1.5 illumination. [ABSTRACT FROM AUTHOR]

New ruthenium complexes based on bipyiridine and terpyridyne type ligands, containing boronic acid functions, of formulae: [Ru(bpy-Φ-B(OH)2)2(CN)2], 6, (bpy-Φ-B(OH)2 = 4-(2,2′-dipyridil)phenylboronic acid), [Ru(trpy-B(OH)2)(tb2bpy)Cl](PF6), 11, (trpy-B(OH)2 = 4-[4′-(2,2′:6′,2″-terpyridil]-boronic acid), [Ru(trpy)-Φ-B(OH)2)(tb2bpy)Cl] (PF6), 12, (trpy)-Φ-B(OH)2 = 4-[4′-(2,2′:6′,2″-terpyridil]-phenylboronic acid), have been prepared, characterized, and tested in dye-sensitized solar cells (DSSCs). The results of this first study indicate that: (i) the boronic acid function acts as interlocking group between sensitizer and mesoporous titanium dioxide; (ii) only the presence of two B(OH)2 groups/molecule allow to obtain high photoanode surface coverages with optical densities > 1; (iii) The presence of the phenyl spacer in 12 reduces the photocurrent efficiency with respect to complex 11, most probably for a reduced electronic coupling between excited sensitizer and semiconductor conduction band. The insights gained from this work suggest that better photoelectrochemical performances should be obtained with dye molecules based on bpy type ligands bearing two boronic acid functions directly bound to the aromatic ring. [Copyright &y& Elsevier]

In view of developing photoelectrosynthetic cells which are able to store solar energy in chemical bonds, water splitting is usually the reaction of choice when targeting hydrogen production. However, alternative approaches can be considered, aimed at substituting the anodic reaction of water oxidation with more commercially capitalizable oxidations. Among them, the production of bromine from bromide ions was investigated long back in the 1980s by Texas Instruments. Herein we present optimized perylene-diimide (PDI)-sensitized antimony-doped tin oxide (ATO) photoanodes enabling the photoinduced HBr splitting with >4 mA/cm 2 photocurrent densities under 0.1 W/cm 2 AM1.5G illumination and 91 ± 3% faradaic efficiencies for bromine production. These remarkable results, among the best currently reported for the photoelectrochemical Br - oxidation by dye sensitized photoanodes, are strongly related to the occupancy extent of ATO's intragap (IG) states, generated upon Sb-doping, as demonstrated by comparing their performances with PDI-sensitized analogues on both undoped SnO 2 - and TiO 2 -passivated ATO scaffolds by means of (spectro)electrochemistry and electrochemical impedance spectroscopy. The architecture of the ATO-PDI photoanodic assembly was further modified via the introduction of a molecular iridium-based water oxidation catalyst, thus proving the versatility of the proposed hybrid interfaces as photoanodic platforms for photoinduced oxidations in PEC devices.

Contamination by pharmaceuticals adversely affects the quality of natural water, causing environmental and health concerns. In this study, target drugs (oxazepam, OZ, 17-α-ethinylestradiol, EE2, and drospirenone, DRO), which have been extensively detected in the effluents of WWTPs over the past decades, were selected. We report here a new photoactive system, operating under visible light, capable of degrading EE2, OZ and DRO in water. The photocatalytic system comprised glass spheres coated with nanostructured, solvothermally treated WO 3 that improves the ease of handling of the photocatalyst and allows for the implementation of a continuous flow process. The photocatalytic system based on solvothermal WO 3 shows much better results in terms of photocurrent generation and photocatalyst stability with respect to state-of-the-art WO 3 nanoparticles. Results herein obtained demonstrate that the proposed flow system is a promising prototype for enhanced contaminant degradation exploiting advanced oxidation processes.

This study investigates the utilization of the conductive polymer poly(3,4-ethylenedioxythiophene) (PEDOT) as a catalytic material for the 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA). PEDOT films doped with different counterions were electrodeposited on graphite foil. In particular, the mobile anion perchlorate and the polymeric ionomers polystyrenesulfonate, Nafion, and Aquivion were used. The electrocatalytic properties of PEDOT films were evaluated toward the TEMPO redox mediator in the absence and the presence of HMF as a substrate for oxidation reactions. The electrocatalytic HMF oxidation was confirmed to occur at PEDOT electrodes, and it was also found that the chemical nature of PEDOT counterions controls the electrocatalytic conversion of HMF by modulating the kinetics of the electrochemical generation of the oxoammonium cation TEMPO(+). Potentiostatic electrolysis experiments showed that both the reference graphite electrode and PEDOT substrates were able to convert HMF to FDCA with an 80% faradaic efficiency (FE) and a >90% yield (FDCA), but, compared to graphite, the complete conversion of HMF to FDCA required a ca. 30% shorter time when using PEDOT electrodes doped with perchlorate or Aquivion, thanks to their ability to sustain a higher current density in the initial phase of the electrolysis. In addition, while all PEDOT films were chemically stable under the electrochemical conditions herein described, only PEDOT films doped with Aquivion were also mechanically robust and stable against delamination. Thus, the new PEDOT/Aquivion composite may represent the best choice for the implementation of PEDOT-based electrodes in TEMPO-mediated electrocatalytic applications.

A new family of ionic Ir(III) cyclometalated complexes with general formula [Ir(CN) 2 (NN)][Br], was designed and prepared to be assessed as photocalysts for the visible light assisted ATRP polymerization of MMA. To this purpose, our design strategy involved both: i) the decoration of the cyclometalating (CN) and the ancillary (NN) ligands with various electron withdrawing and/or electron donor substituents and, ii) the use of Br - as the counter anion for these cationic Ir(III) species. After an extensive screening in which the [Ir(CN) 2 (NN)][Br]-type compounds were compared to the model neutral complex fac-[Ir(ppy) 3 ], the "fully" amino-substituted ion pairs abbreviated as [10][Br] and [11][Br], exhibited the best photocatalytic performances under irradiation with CFL lamps. It is worth noting that the outcomes of transient absorption spectroscopy (TAS) experiments combined with theoretical DFT calculations, enlightened the role played by the Ir(III) complexes in the mechanism of the photoATRP process, and suggested the rationalization of the different performances that were highlighted by our Ir(III) catalyst in the visible light assisted photopolymerization of MMA., (© 2024 Wiley-VCH GmbH.)

High energy resolution fluorescence detected X-ray absorption spectroscopy is a powerful method for probing the electronic structure of functional materials. The X-ray penetration depth and photon-in/photon-out nature of the method allow operando experiments to be performed, in particular in electrochemical cells. Here, operando high-resolution X-ray absorption measurements of a BiVO 4 photoanode are reported, simultaneously probing the local electronic states of both cations. Small but significant variations of the spectral lineshapes induced by the applied potential were observed and an explanation in terms of the occupation of electronic states at or near the band edges is proposed., (open access.)

Supercapacitors offer notable properties as energy storage devices, providing high power density and fast charging and discharging while maintaining a long cycling lifetime. Although poly(3,4-ethylenedioxythiophene) doped with poly(4-styrenesulfonate) (PEDOT/PSS) has become a gold standard among organic electronics materials, researchers are still investigating ways to further improve its capacitive characteristics. In this work, we introduced Nafion as an alternative polymeric counterion to PSS to form highly capacitive PEDOT/Nafion; its advantageous supercapacitive properties were further improved by treatment with either dimethyl sulfoxide or ethylene glycol. Accordingly, electrochemical characterization of PEDOT/Nafion films revealed their high areal capacitance (22 mF cm -2 at 10 mV/s) and low charge transfer resistance (∼380 Ω), together with excellent volumetric capacitance (74 F cm -3 ), Coulombic efficiency (99%), and an energy density of 23.1 ± 1.5 mWh cm -3 at a power density of 0.5 W cm -3 , resulting from a more effective ion diffusion inside the conductive film, as confirmed by the results of spectroscopic studies. A proof-of-concept symmetric supercapacitor based on PEDOT/Nafion was characterized with a specific capacitance of approximately 15.7 F g -1 and impressive long-term stability (Coulombic efficiency ∼99% and capacitance ∼98.7% after 1000 charging/discharging cycles), overperforming the device based on PEDOT/PSS.

This research introduces a novel series of perfluorinated Zn(II) porphyrins with positive oxidation potentials designed as sensitizers for photoelectrosynthetic cells, with a focus on promoting the oxidation of benzyl alcohol (BzOH) mediated by the 2,2,6,6-tetramethyl-1-piperidine N -oxyl (TEMPO) organocatalyst. Three dyes, CLICK-3 , CLICK-4 , and BETA-4 , are meticulously designed to explore the impact of substituents and their positions on the perfluorinated porphyrin ring in terms of redox potentials and energy level alignment when coupled with SnO 2 /TiO 2 -based photoanodes and TEMPO mediator. A comprehensive analysis utilizing spectroscopy, electrochemistry, photophysics, and computational techniques of the dyes in solution and sensitized thin films unveils an enhanced charge-separation character in the 4D-π-1A type BETA-4 . Incorporating four dimethylamino donor groups at the periphery of the porphyrin ring and a BTD-accepting linker at the β-pyrrolic position equips the structure with a more efficient donor-acceptor system. This enhancement ensures improved light-harvesting capacity, resulting in a doubled incident photon-to-current conversion efficiency (IPCE% ≃30%) in the presence of LiI compared to meso -substituted dyes CLICK-3 and CLICK-4 . Sensitizing SnO 2 /TiO 2 thin films with BETA-4 successfully promotes the photooxidation of benzyl alcohol (BzOH) in the presence of the rapid TEMPO radical catalyst, yielding photocurrents of approximately 125 μA/cm 2 in an optimized TBPy/LiClO 4 /ACN electrolyte. Notably, when lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) replaces TBPy as the base for TEMPO-catalyzed BzOH oxidation, a remarkable photocurrent of around 800 μA/cm 2 is achieved, marking one of the highest values reported for this photoelectrochemical reaction to date. This study underscores that the proper functionalization of perfluorinated zinc porphyrins positions these dyes as ideal candidates for sensitizing SnO 2 /TiO 2 in the photodriven oxidation of BzOH. It also highlights the crucial role of carefully tuning electrolyte composition based on the electronic properties of molecular sensitizers.

ConspectusThe harvesting and conversion of solar energy have become a burning issue for our modern societies seeking to move away from the exploitation of fossil fuels. In this context, dye-sensitized solar cells (DSSCs) have proven to be trustworthy alternatives to silicon-based cells with advantages in terms of transparency and efficiency under low illumination conditions. These devices are highly dependent on the ability of the sensitizer that they contain to collect sunlight and transfer an electron to a semiconductor after excitation. Ruthenium and polypyridine complexes are benchmarks in this field as they exhibit ideal characteristics such as long-lasting metal-ligand charge transfer (MLCT) states and efficient separation between electrons and holes, limiting recombination at the dye-semiconductor interface. Despite all of these advantages, ruthenium is a noble metal, and the development of more sustainable energy devices based on earth-abundant metals is now a must. A quick glance at the periodic table reveals iron as a potential good candidate, since it belongs to the same group of ruthenium, which suggests similar electronic properties. However, striking photophysical differences exist between ruthenium(II) polypyridyl complexes and their Fe(II) analogues, the latter suffering from short-lived MLCT states resulting of their ultrafast relaxation into metal-centered (MC) states. Pyridyl-N-heterocyclic carbenes (pyridylNHC) brought a strong σ-donor character required to promote a higher ligand field splitting of the iron d orbitals. This induces destabilization of the MC states over the MLCT manifold and a consequent slowdown of the excited states deactivation providing iron(II) complexes with tens of picoseconds lifetimes, making them more promising for applications in DSSCs. This Account highlights our recent advances in the development and characterization of iron-sensitized solar cells (FeSSCs) with a focus on the design of efficient sensitizers going from homoleptic to heteroleptic complexes (bearing different anchoring groups) and the tuning of electrolyte composition. Our rational approach led to the best photocurrent and efficiency ever reported for an iron sensitized solar cell (2% PCE and 9 mA/cm 2 ) using a cosensitization process. This work clearly evidences that the solar energy conversion based on iron complex sensitization is now an opened and fruitful route.

Since Mallouk's earliest contribution, dye-sensitized photoelectrochemical cells (DSPECs) have emerged as a promising class of photoelectrochemical devices capable of storing solar light into chemical bonds. This review primarily focuses on metal complexes outlining stabilization strategies and applications. The ubiquity and safety of water have made its splitting an extensively studied reaction; here, we present some examples from the outset to recent advancements. Additionally, alternative oxidative pathways like HX splitting and organic reactions mediated by a redox shuttle are discussed.

The phosphine ligand (Ph 2 PCH 2 N(CH 3 )(CH 2 ) 2 Ph, PNMPEA) obtained by the reaction of the (hydroxymethyl)diphenylphosphine with naturally occurring alkaloid N-methylphenethylamine, was used to synthesize the half-sandwich iridium(III) (Ir(η 5 -Cp*)Cl 2 Ph 2 PCH 2 N(CH 3 )(CH 2 ) 2 Ph, IrPNMPEA) and ruthenium(II) (Ru(η 6 -p-cymene)Cl 2 Ph 2 PCH 2 N(CH 3 )(CH 2 ) 2 Ph, RuPNMPEA) complexes. They were characterized using a vast array of methods, including 1D and 2D NMR, ESI(+)MS spectrometry, elemental analysis, cyclic voltammetry (CV), electron spectroscopy in the UV-Vis range (absorption, fluorescence) and density functional theory (DFT). The initial antimicrobial activity in vitro toward Gram-positive and Gram-negative bacterial strains was examined, indicating that both complexes are selective towards Gram-positive bacteria, e. g., Staphylococcus aureus, where the IrPNMPEA has been more bactericidal compared to RuPNMPEA. Additionally, the interactions of these compounds with various biomolecules, such as DNA (ctDNA, plasmid DNA, 9-ethylguanine (9-EtG), and 9-methyladenine (9-MeA)), nicotinamide adenine dinucleotide (NADH), glutathione (GSH), and ascorbic acid (Asc) were described. The results showed that both Ir(III) and Ru(II) complexes accelerate the oxidation process of NADH, GSH and Asc that appeared to occur by an electron transfer mechanism. Interestingly, only IrPNMPEA leads to the formation of various biomolecule adducts, which can explain its higher activity. Furthermore, RuPNMPEA and IrPNMPEA have been interacting with the DNA through weak noncovalent interactions., (© 2023 Wiley-VCH GmbH.)

Intensity-modulated photocurrent spectroscopy (IMPS) has been largely employed in semiconductor characterization for solar energy conversion devices to probe the operando behavior with widely available facilities. However, the implementation of IMPS data analysis to complex structures, whether based on the physical rate constant model (RCM) or the assumption-free distribution of relaxation times (DRT), is generally limited to a semi-quantitative description of the charge carrier kinetics of the system. In this study, a new algorithm for the analysis of IMPS data is developed, providing unprecedented time resolution to the investigation of μs to s charge carrier dynamics in semiconductor-based systems used in photoelectrochemistry and photovoltaics. The algorithm, based on the previously developed DRT analysis, is herein modified with a Lasso regression method and available to the reader free of charge. A validation of this new algorithm is performed on a α-Fe 2 O 3 photoanode for photoelectrochemical water splitting, identified as a standard platform in the field, highlighting multiple potential-dependent charge transfer paths, otherwise hidden in the conventional IMPS data analysis., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Fe(ii) pyridyl-NHC sensitizers bearing thienylcyanoacrylic (ThCA) anchoring groups have been designed and characterized with the aim of enhancing the metal to surface charge separation and the light harvesting window in iron-sensitized DSSCs (FeSSCs). In these new Fe(ii) dyes, the introduction of the ThCA moiety remarkably extended the spectral response and the photocurrent, in comparison with their carboxylic analogues. The co-sensitization based on a mixture of a carboxylic and a ThCA-iron complex produced a panchromatic absorption, up to 800 nm and the best photocurrent and efficiency ( J sc : 9 mA cm -2 and PCE: 2%) ever reported for an FeSSC., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Dye-sensitized photoanodes for C-H activation in organic substrates are assembled by vacuum sublimation of a commercially available quinacridone (QNC) dye in the form of nanosized rods onto fluorine-doped tin oxide (FTO), TiO 2 , and SnO 2 slides. The photoanodes display extended absorption in the visible range (450-600 nm) and ultrafast photoinduced electron injection (<1 ps, as revealed by transient absorption spectroscopy) of the QNC dye into the semiconductor. The proton-coupled electron-transfer reactivity of QNC is exploited for generating a nitrogen-based radical as its oxidized form, which is competent in C-H bond activation. The key reactivity parameter is the bond-dissociation free energy (BDFE) associated with the N⋅/N-H couple in QNC of 80.5±2.3 kcal mol -1 , which enables hydrogen atom abstraction from allylic or benzylic C-H moieties. A photoelectrochemical response is indeed observed for organic substrates characterized by C-H bonds with BDFE below the 80.5 kcal mol -1 threshold, such as γ-terpinene, xanthene, or dihydroanthracene. This work provides a rational, mechanistically oriented route to the design of dye-sensitized photoelectrodes for selective organic transformations., (© 2022 Wiley-VCH GmbH.)

A good photocatalyst maximizes the absorption of excitation light while reducing the recombination of photogenerated carriers. Among visible light responsive materials, CdS has good carrier transport capacity; however, its photostability is poor and limits its use. Here, the synthesis of a new hydrothermal CdS is reported, and post-synthesis annealing determines crystal properties and spectroscopic characteristics. The introduction of sulfur vacancies as intra band gap states is the key factor for the enhancement of photocatalytic activity. In fact, by spectroscopic and photo-electrochemical experiments, we demonstrate that sulfur vacancies act as an electron sink, favoring the charge transfer process to methyl orange. In addition, the studied hydrothermal CdS is characterized by very high stability, thus enabling a visible-light active photocatalyst that is overall recyclable, stable and more efficient than the commercial benchmark.

Novel heteronuclear Ir III -Cu II coordination compounds ([Ir(η 5 -Cp*)Cl 2 Pcfx-Cu(phen)](NO 3 )·1.75(CH 3 OH)·0.75(H 2 O) ( 1 ), [Ir(η 5 -Cp*)Cl 2 Pnfx-Cu(phen)](NO 3 )·1.75(CH 3 OH)·0.75(H 2 O) ( 2 ), [Ir(η 5 -Cp*)Cl 2 Plfx-Cu(phen)](NO 3 )·1.3(H 2 O)·1.95(CH 3 OH) ( 3 ), [Ir(η 5 -Cp*)Cl 2 Psfx-Cu(phen)] ( 4 )) bearing phosphines derived from fluoroquinolones, namely, sparfloxacin (Hsfx), ciprofloxacin (Hcfx), lomefloxacin (Hlfx), and norfloxacin (Hnfx), have been synthesized and studied as possible anticancer chemotherapeutics. All compounds have been characterized by electrospray ionization mass spectrometry (ESI-MS), a number of spectroscopic methods ( i . e ., IR, fluorescence, and electron paramagnetic resonance (EPR)), cyclic voltammetry, variable-temperature magnetic susceptibility measurements, and X-ray diffractometry. The coordination geometry of Ir III in all complexes adopts a characteristic piano-stool geometry with the η 5 -coordinated and three additional sites occupied by two chloride and phosphine ligands, while Cu II ions in complexes 1 and 2 form a distorted square-pyramidal coordination geometry, and in complex 3 , the coordination geometry around Cu II ions is a distorted octahedron. Interestingly, the crystal structure of [Ir(η 5 -Cp*)Cl 2 Plfx-Cu(phen)] features the one-dimensional (1D) metal-organic polymer. Liposomes loaded with redox-active and fluorescent [Ir(η 5 -Cp*)Cl 2 Pcfx-Cu(phen)] ( 1L ) have been prepared to increase water solubility and minimize serious systemic side effects. It has been proven, by confocal microscopy and an inductively coupled plasma mass spectrometry (ICP-MS) analysis, that the liposomal form of compound 1 can be effectively accumulated inside human lung adenocarcinoma and human prostate carcinoma cells with selective localization in nuclei. A cytometric analysis showed dominance of apoptosis over the other cell death types. Furthermore, the investigated nanoformulations induced changes in the cell cycle, leading to S phase arrest in a dose-dependent manner. Importantly, in vitro anticancer action on three-dimensional (3D) multicellular tumor spheroids has been demonstrated.