Low and High Molecular Mass Anthraquinone Derivatives Containing Substituents of Varying Electron Donating Properties: Electrochemical and Spectroelectrochemical Properties.

Two series of donor-acceptor compounds were investigated, consisting of the same anthraquinone acceptor substituted in either position 1 or in position 2 with donors of varying electron donating properties, namely, phenoxazine (Anth-1-Phenox and Anth-2-Phenox), carbazole (Anth-1-Carb and Anth-2-Carb), or diphenylamine (Anth-1-NPh2 and Anth-2-NPh2). In the negative potential range (vs Fc/Fc) all studied compounds exhibited two reversible redox couples corresponding to two 1e reductions of the anthraquinone unit. These reduction processes showed very little dependence on the donor chemical nature and the positional isomerism, yielding (0/-1) in the range from -1.

Cobalt Oxide (CoO) Thin Films Synthesized by Atmospheric Pressure PECVD: Deposition Mechanisms and Catalytic Potential.

Crystalline and electrocatalytically active cobalt oxide (CoO) thin films were successfully synthesized under open-air conditions using atmospheric pressure plasma-enhanced chemical vapor deposition (AP-PECVD) with the Co-(acac) precursor. This study explored the influence of process parameters on the composition, crystallinity, and quality of the resulting thin films. It was found that the substrate temperature had a negligible effect due to the inherent heating by the plasma afterglow.

Engineering Nickel(II) Porphyrin-Conjugated Polymers with Different Aryl -Substituents for n-Type and p-Type Ammonia Sensors.

Conjugated polymers have revolutionized the field of conductometric gas sensors for sensing toxic gases arising from the fast urbanization and industrialization. In this work, we report the synthesis of a series of 5,15-diaryl Ni(II) porphyrin-conjugated polymers () and their integration as the top layer on an octafluorinated copper phthalocyanine () sublayer to construct bilayer heterojunction (BLH) devices for ammonia sensing. For the first time, we report the pioneering demonstration of polarity engineering within a BLH device by manipulating the -substituent of the 5,15-diaryl Ni(II) porphyrin-conjugated polymer constituting the top layer of the BLH device.

Triflate Salts as Alternative Non-Chlorinated Oxidants for the Oxidative Chemical Vapor Deposition and Electronic Engineering of Conjugated Polymers.

Oxidative chemical vapor deposition (oCVD) stands as an attractive approach for the synthesis, engineering, and integration of conjugated polymers for advanced electronic and optoelectronic applications. In oCVD, the oxidant significantly influences the conformational and optoelectronic properties of the resulting conjugated polymer thin films. In this work, triflate salts of iron(III) and copper(II) (Fe(OTf) and Cu(OTf), respectively) are investigated for the first time as suitable alternative oxidants to the widely used iron(III) chloride (FeCl) for the oCVD of conjugated polymers.

Directly-Fused Ni(II)Porphyrin Conjugated Polymers with Blocked meso-Positions: Impact on Electrocatalytic Properties.

The oxidative coupling reaction of two Ni(II) porphyrins meso-substituted with three and four phenyl groups, Ni(II) 5,10,15-(triphenyl)porphyrin (NiPhP) and Ni(II) 5,10,15,20-(tetraphenyl)porphyrin (NiPhP) respectively, was investigated in a oxidative chemical vapor deposition (oCVD) process. Irrespective of the number of meso-substituents, high-resolution mass spectrometry evidences the formation of oligomeric species containing up to five porphyrin units. UV-Vis-NIR and XPS analyses of the oCVD films highlighted a strong dependence of the intermolecular coupling reaction with the substrate temperature.

A Polymer-Derived Co(Fe)O Oxygen Evolution Catalyst Benefiting from the Oxidative Dehydrogenative Coupling of Cobalt Porphyrins.

Thin films of cobalt porphyrin conjugated polymers bearing different substituents are prepared by oxidative chemical vapor deposition (oCVD) and investigated as heterogeneous electrocatalysts for the oxygen evolution reaction (OER). Interestingly, the electrocatalytic activity originates from polymer-derived, highly transparent Co(Fe)O species formed under operational alkaline conditions. Structural, compositional, electrical, and electrochemical characterizations reveal that the newly formed active catalyst greatly benefited from both the polymeric conformation of the porphyrin-based thin film and the inclusion of the iron-based species originating from the oCVD reaction.

Enhanced Photocatalytic Hydrogen Evolution from Water Splitting on TaO/SrZrO Heterostructures Decorated with CuO/RuO Cocatalysts.

Photocatalytic H generation by water splitting is a promising alternative for producing renewable fuels. This work synthesized a new type of TaO/SrZrO heterostructure with Ru and Cu (RuO/CuO/TaO/SrZrO) using solid-state chemistry methods to achieve a high H production of 5164 μmol g h under simulated solar light, 39 times higher than that produced using SrZrO. The heterostructure performance is compared with other TaO/SrZrO heterostructure compositions loaded with RuO, CuO, or Pt.

Electronic and energy level engineering of directly fused porphyrin-conjugated polymers - impact of the central metal cation.

The integration of porphyrins and their derivatives in functional devices for solar-assisted fuel production is both highly attractive and challenging due to the difficulties in processing them. This limitation is overcome in the gas-phase approach, particularly by oxidative chemical vapor deposition (oCVD), leading to the simultaneous synthesis and deposition of conjugated porphyrin coatings. We have investigated the impact of the metal cation of 5,15-diphenyl metalloporphyrins (MDPP; M = Co, Cu, Mg, Zn, Pd, Pt, Ag, Ru, Ag, and FeCl) on the dehydrogenative coupling reaction leading to fused-metalloporphyrin thin films oCVD and on the optoelectronic properties of the resulting thin films.

Low Temperature Open-Air Plasma Deposition of SrTiO Films for Solar Energy Harvesting: Impact of Precursors on the Properties and Performances.

Strontium titanate (STO) is a well-known oxide used in a wide variety of applications due to its excellent stability and optoelectronic properties. However, its integration in photoelectrocatalytic devices is limited by the lack of fast and scalable methods to produce robust films at a low temperature and atmospheric pressure. Herein, we report an atmospheric pressure plasma-enhanced chemical vapor deposition (AP-PECVD) approach for the synthesis of STO crystalline films and their applications for photoelectrochemical solar energy conversion.

Fused Metalloporphyrin Thin Film with Tunable Porosity via Chemical Vapor Deposition.

Porous and highly conjugated multiply fused porphyrin thin films are prepared from a fast and single-step chemical vapor deposition approach. While the solution-based coupling of porphyrins is usually undertaken at room temperature, the gas phase reaction of nickel(II) 5,15-(diphenyl)porphyrin and iron(III) chloride (FeCl) is investigated for temperatures as high as 200 °C. Helium ion and atomic force microscopy, supported by weight and thickness measurements, shows a drastic decrease of the fused porphyrin thin film's density accompanied by the formation of a mesoporous morphology upon increase of the reaction temperature.

Molecular flattening effect to enhance the conductivity of fused porphyrin tape thin films.

The straightforward synthesis of directly fused porphyrins (porphyrin tapes) from 5,15-diphenyl porphyrinato nickel(ii) complexes with different substituents on the phenyl rings is achieved while processing from the gas phase. The porphyrin tapes, exhibiting NIR absorption, are readily obtained in thin film form. The gas phase approach cuts the need for solubilizing groups allowing for the first time the study of their conductivity according to the substituent.

Reactivity of Nickel(II) Porphyrins in oCVD Processes-Polymerisation, Intramolecular Cyclisation and Chlorination.

Oxidative chemical vapour deposition of (5,15-diphenylporphyrinato)nickel(II) (NiDPP) with iron(III) chloride as oxidant yielded a conjugated poly(metalloporphyrin) as a highly coloured thin film, which is potentially useful for optoelectronic applications. This study clarified the reactive sites of the porphyrin monomer NiDPP by HRMS, UV/Vis/NIR spectroscopy, cyclic voltammetry and EPR spectroscopy in combination with quantum chemical calculations. Unsubstituted meso positions are essential for successful polymerisation, as demonstrated by varying the porphyrin meso substituent pattern from di- to tri- and tetraphenyl substitution.

Conductive Fused Porphyrin Tapes on Sensitive Substrates by a Chemical Vapor Deposition Approach.

Oxidative polymerization of nickel(II) 5,15-diphenyl porphyrin and nickel(II) 5,15-bis(di-3,5-tert-butylphenyl) porphyrin by oxidative chemical vapor deposition (oCVD) yields multiply fused porphyrin oligomers in thin film form. The oCVD technique enables one-step formation, deposition, and p-doping of conjugated poly(porphyrins) coatings without solvents or post-treatments. The decisive reactions and side reactions during the oCVD process are shown by high-resolution mass spectrometry.

Thermoresponsive Water-Soluble Polymer Layers and Water-Stable Copolymer Layers Synthesized by Atmospheric Plasma Initiated Chemical Vapor Deposition.

The growth of thermoresponsive layers with the atmospheric pressure plasma-initiated chemical vapor deposition (AP-PiCVD) process is reported for the first time. N-vinyl caprolactam (NVCL) was successfully homopolymerized and copolymerized with ethylene glycol dimethacrylate (EGDMA), yielding water-soluble and water-stable thermoresponsive thin films, respectively. Strong chemical retention and high thermoresponsivity were achieved, highlighting the ability of AP-PiCVD to grow functional conventional homopolymers and copolymers.

Precursors for Atmospheric Plasma-Enhanced Sintering: Low-Temperature Inkjet Printing of Conductive Copper.

Bidentate diamine and amino-alcohol ligands have been used to form solid, water-soluble, and air-stable monomeric copper complexes of the type [Cu(NHCHCH(R)Y)(NO)] (, R=H, Y=NH; , R=H, Y=OH; , R=Me, Y=OH). The complexes were characterized by elemental analysis, mass spectrometry, infrared spectroscopy, thermal gravimetric analysis, and single-crystal X-ray diffraction. Irrespective of their decomposition temperature, precursors - yield highly conductive copper features [1.

Transparent anti-fogging and self-cleaning TiO/SiO thin films on polymer substrates using atmospheric plasma.

Transparent anti-fogging and self-cleaning coatings are of great interest for many applications, including solar panels, windshields and displays or lenses to be used in humid environments. In this paper, we report on the simultaneous synthesis, at atmospheric pressure, of anatase TiO nanoparticles and low-temperature, high-rate deposition of anatase TiO/SiO nanocomposite coatings. These coatings exhibit durable super-hydrophilic and photocatalytic properties.

Significance of a Noble Metal Nanolayer on the UV and Visible Light Photocatalytic Activity of Anatase TiO Thin Films Grown from a Scalable PECVD/PVD Approach.

UV and visible light photocatalytic composite Pt and Au-TiO coatings have been deposited on silicon and glass substrates at low temperature using a hybrid ECWR-PECVD/MS-PVD process. Methylene blue, stearic acid, and sulfamethoxazole were used as dye, organic, and antibiotic model pollutants, respectively, to demonstrate the efficiency of these nanocomposite coatings for water decontamination or self-cleaning surfaces applications. Raman investigations revealed the formation of anatase polymorph of TiO in all synthesized coatings with a shifting of the main vibrational mode peak to higher wavenumber in the case of Au-TiO coating, indicating an increase number of crystalline defects within this coating.

Photocatalytic Anatase TiO Thin Films on Polymer Optical Fiber Using Atmospheric-Pressure Plasma.

Due to the undeniable industrial advantages of low-temperature atmospheric-pressure plasma processes, such as low cost, low temperature, easy implementation, and in-line process capabilities, they have become the most promising next-generation candidate system for replacing thermal chemical vapor deposition or wet chemical processes for the deposition of functional coatings. In the work detailed in this article, photocatalytic anatase TiO thin films were deposited at a low temperature on polymer optical fibers using an atmospheric-pressure plasma process. This method overcomes the challenge of forming crystalline transition metal oxide coatings on polymer substrates by using a dry and up-scalable method.

Interstitial Boron-Doped TiO2 Thin Films: The Significant Effect of Boron on TiO2 Coatings Grown by Atmospheric Pressure Chemical Vapor Deposition.

The work presented here describes the preparation of transparent interstitial boron-doped TiO2 thin-films by atmospheric pressure chemical vapor deposition (APCVD). The interstitial boron-doping, on TiO2, proved by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD), is shown to enhance the crystallinity and significantly improve the photocatalytic activity of the TiO2 films. The synthesis, highly suitable for a reel-to-reel process, has been carried out in one step.

Metal-Organic Covalent Network Chemical Vapor Deposition for Gas Separation.

The chemical vapor deposition (CVD) polymerization of metalloporphyrin building units is demonstrated to provide an easily up-scalable one-step method toward the deposition of a new class of dense and defect-free metal-organic covalent network (MOCN) layers. The resulting hyper-thin and flexible MOCN layers exhibit outstanding gas-separation performances for multiple gas pairs.

Atmospheric pressure plasma-initiated chemical vapor deposition (AP-PiCVD) of poly(diethylallylphosphate) coating: a char-forming protective coating for cellulosic textile.

An innovative atmospheric pressure chemical vapor deposition method toward the deposition of polymeric layers has been developed. This latter involves the use of a nanopulsed plasma discharge to initiate the free-radical polymerization of an allyl monomer containing phosphorus (diethylallylphosphate, DEAP) at atmospheric pressure. The polymeric structure of the film is evidence by mass spectrometry.

Dual application of (aqua)(chlorido)(porphyrinato)chromium(III) as hypersensitive amine-triggered ON switch and for dioxygen activation.

Although synthesis and substitution reactions of chlorido chromium(III) porphyrins Cr(III)(TPP)(Cl)(L) (H2TPP = 5,10,15,20-tetraphenyl porphyrin, L = pyridine, H2O, ROH, etc.), have been well-established in coordination chemistry for decades, an unexpected dichotomous reactivity of Cr(III)(TPP)(Cl)(H2O) (1) toward amines is disclosed here. This reactivity leads to the application of 1 as highly sensitive substoichiometric and irreversible ON switch for amine detection by an autocatalytic pathway.

Robust bio-inspired antibacterial surfaces based on the covalent binding of peptides on functional atmospheric plasma thin films.

Here, we describe a robust process aiming at conferring antibacterial properties on stainless steel through the covalent grafting of nisin, a natural antimicrobial peptide, onto a functional plasma thin film deposited by an atmospheric pressure dielectric barrier discharge process. The three different steps of the procedure, namely the deposition of a carboxyl rich thin layer, the surface activation by using a zero-length crosslinking agent and the nisin immobilisation, are reported and thoroughly characterised. A correlation between the carboxylic group surface concentration and the surface roughness onto the antibacterial properties of the layers is evidenced.

A novel dry chemical path way for diene and dienophile surface functionalization toward thermally responsive metal-polymer adhesion.

In this paper, we report a new and easily up-scalable dry chemical method to functionalize with diene and dienophile groups a large range of surfaces, such as metal, polymer, or glass, and we demonstrate the potentiality of this technique to realize thermally responsive adhesion between these materials. A complete and extensive surface chemistry analysis of the grafted surfaces, based on the deposition of an anhydride-rich thin plasma polymer layer by using an atmospheric pressure dielectric barrier discharge (DBD) plasma process, and its subsequent gas phase aminolysis reaction with specific diene or dienophile compound is discussed. The optimization of the assembling condition for these tailored surfaces has led to achieve a Diels-Alder adhesion force up to 0.

Single-step process for the deposition of high water contact angle and high water sliding angle surfaces by atmospheric pressure dielectric barrier discharge.

Fluorine-free surfaces with high water contact angle (WCA) and high adhesion force to water are prepared by the atmospheric pressure dielectric barrier discharge (AP-DBD) of hexamethyldisiloxane on cold rolled aluminum foil. Water droplets, which remained on the plasma-polymerized hexamethyldisiloxane (ppHMDSO) surface with contact angle of 155°, do not slide even when the surface is tilted vertically or turned upside down. Scanning electron microscopy, atomic force microscopy and confocal microscopy highlight the importance of the dual-scale roughness of the ppHMDSO surface.