Florent Yang

Solar hydrogen evolution using metal-free photocatalytic polymeric carbon nitride/CuInS2 composites as photocathodes

Polymeric carbon nitride (g-C3N4) films were synthesized on polycrystalline semiconductor CuInS2 chalcopyrite thin film electrodes by thermal polycondensation and were investigated as photocathodes for the hydrogen evolution reaction (HER) under photoelectrochemical conditions. The composite photocathode materials were compared to g-C3N4 powders and were characterized with grazing incidence X-ray diffraction and X-ray photoemission spectroscopy as well as Fourier transform infrared and Raman spectroscopies. Surface modification of polycrystalline CuInS2 semiconducting thin films with photocatalytically active g-C3N4 films revealed structural and chemical properties corresponding to the properties of g-C3N4 powders. The g-C3N4/CuInS2 composite photocathode material generates a cathodic photocurrent at potentials up to +0.36 V vs. RHE in 0.1 M H2SO4 aqueous solution (pH 1), which corresponds to a +0.15 V higher onset potential of cathodic photocurrent than the unmodified CuInS2 semiconducting thin film photocathodes. The cathodic photocurrent for the modified composite photocathode materials was reduced by almost 60% at the hydrogen redox potential. However, the photocurrent generated from the g-C3N4/CuInS2 composite electrode was stable for 22 h. Therefore, the presence of the polymeric g-C3N4 films composed of a network of nanoporous crystallites strongly protects the CuInS2 semiconducting substrate from degradation and photocorrosion under acidic conditions. Conversion of visible light to hydrogen by photoelectrochemical water splitting can thus be successfully achieved by g-C3N4 films synthesized on polycrystalline CuInS2 chalcopyrite electrodes.

Tunable optical transition in polymeric carbon nitrides synthesized via bulk thermal condensation

Polymeric derivatives of dicyandiamide were synthesized via a bulk thermal condensation method, using a range of process temperatures between 400 and 610 °C. The obtained carbon nitride powders exhibit an optical transition in the UV-green range that has been assigned to the direct bandgap of a semiconductor-like material. Within this context, the apparent bandgap is linearly tunable with increasing process temperatures, showing a temperature coefficient of - 1.7(1) meV K(-1) between 2.5 and 3.0 eV. The obtained results show a predominant optical transition within the tri-s-triazine unit of the polymer, with a bathochromic shift originating from a gradually increasing degree of polymerization.

Metal-Free Photocatalytic Graphitic Carbon Nitride on p-Type Chalcopyrite as a Composite Photocathode for Light-Induced Hydrogen Evolution

Recently, it has been shown that an abundant material, polymeric carbon nitride, can produce hydrogen from water under visible-light irradiation in the presence of a sacrificial donor. We present herein the preparation and characterization of graphitic carbon nitride (g-C(3)N(4)) films on p-type semiconducting CuGaSe(2) chalcopyrite thin-film substrates by thermal condensation of a dicyandiamide precursor under inert-gas conditions. Structural and surface morphological studies of the carbon nitride films suggest a high porosity of g-C(3)N(4) thin films consisting of a network of nanocrystallites. Photoelectrochemical investigations show light-induced hydrogen evolution upon cathodic polarization for a wide range of proton concentrations in the aqueous electrolyte. Additionally, synchrotron radiation-based photoelectron spectroscopy has been applied to study the surface/near-surface chemical composition of the utilized g-C(3)N(4) film photocathodes. For the first time, it has been shown that g-C(3)N(4) films coated on p-type CuGaSe(2) thin films can be successfully applied as new photoelectrochemical composite photocathodes for light-induced hydrogen evolution.

Vibrational and Electronic Characterization of Ethynyl Derivatives Grafted onto Hydrogenated Si(111) Surfaces

Covalent grafting of ethynyl derivatives (-C triple bond C-H, -C triple bond C-CH3, -C triple bond C-aryl) onto H-terminated Si(111) surfaces was performed by a one-step anodic treatment in Grignard electrolytes. The electrochemical grafting of such ethynyl derivatives, which tends to form ultrathin polymeric layers, can be controlled by the current and charge flow passing through the Si electrode. The prepared ultrathin layers cover the Si surface and had a thickness up to 20 nm, as investigated by the scanning electron microscopy (SEM) technique. Exchanging Cl for Br in the ethynyl Grignard reagent leads to very thin layers, even under the same electrochemical conditions. However, for all ethynyl derivatives, high-resolution synchrotron X-ray photoelectron spectroscopy (SXPS) investigations reveal the incorporation of halogen atoms in the organic layers obtained. Moreover, it was observed that the larger the end group of the ethynyl derivative, the thinner the thickness of the ultrathin polymeric layers as measured by both SXPS and SEM techniques after low and high current flow respectively. For the first time, these new types of ultrathin organic layers on Si surfaces were investigated using infrared spectroscopic ellipsometry (IRSE). The different possible reaction pathways are discussed.

Anisotropy in Hydrogen-Passivated and Organically Modified Nanoporous Silicon Surfaces Studied by Polarization Dependent IR Spectroscopy

Infrared spectroscopic ellipsometry (IRSE) was applied for characterization of porous silicon (PSi) electrochemically prepared in acidic fluoride solution. When no formation of SiO2 was involved in the preparation, an anisotropic distribution of PSi bonds with the terminating molecules was achieved. On the contrary, oxidation of PSi samples during the preparation led to an isotropic structure. IR spectra obtained from organically functionalized PSi surfaces suggested that the morphology of the organic layer on PSi was anisotropic for electrochemical grafting of methyl but not nitrobenzene. Comparison between the IRSE spectra obtained from PSi and Si(111) surfaces and application of optical models supported these observations.

Graphitic carbon nitride nano-emitters on silicon: a photoelectrochemical heterojunction composed of earth-abundant materials for enhanced evolution of hydrogen

Graphitic carbon nitride is a promising heterogeneous catalyst for light-induced generation of hydrogen. Here, we report the successful formation of nano-scaled carbon nitride structures on silicon, mitigating the known limitations of charge transport within bulky C–N networks. An efficient photoelectrochemical heterojunction is thereby realized, developed from earth-abundant materials only.

Recombination Behaviour at the Ultrathin Polypyrrole Film/Silicon Interface Investigated by In-situ Pulsed Photoluminescence

We investigated the change in Si surface recombination behaviour during the electrodeposition of ultrathin polypyrrole (PPy) films onto Si surfaces by means of in-situ pulsed photoluminescence (PL) spectroscopy. The quenching of the band-gap related PL is lower (better passivation) when the electrodeposition is performed in a less acidic solution by use of potential pulse sequences. In-situ infrared spectroscopic ellipsometry (IR-SE) was applied for the first time to PPy electrodeposition. IR-SE and PL measurements confirm negligible formation of SiOx species at the Si/PPy interface although aqueous electrolytes were used.

ZnO Nanowire Networks as Photoanode Model Systems for Photoelectrochemical Applications

In this work, the fabrication of zinc oxide (ZnO) nanowire networks is presented. By combining ion-track technology, electrochemical deposition, and atomic layer deposition, hierarchical and self-supporting three-dimensional (3D) networks of pure ZnO- and TiO2-coated ZnO nanowires were synthesized. Analysis by means of high-resolution transmission electron microscopy revealed a highly crystalline structure of the electrodeposited ZnO wires and the anatase phase of the TiO2 coating. In photoelectrochemical measurements, the ZnO and ZnO/TiO2 nanowire networks, used as anodes, generated higher photocurrents compared to those produced by their film counterparts. The ZnO/TiO2 nanowire network exhibited the highest photocurrents. However, the protection by the TiO2 coatings against chemical corrosion still needs improvement. The one-dimensionality of the nanowires and the large electrolyte-accessible area make these 3D networks promising photoelectrodes, due to the improved transport properties of photogenerated charge carriers and faster redox reactions at the surface. Moreover, they can find further applications in e.g., sensing, catalytical, and piezoelectric devices.

Characterization of Thin Organic Films with Surface-Sensitive FTIR Spectroscopy

This chapter reviews the role of infrared spectroscopy in characterization of surfaces and interfaces of thin organic films. FTIR spectroscopy is widely utilized in studies of chemical bonds addressing questions concerning organization and orientation of the molecules in those films. In-situ FTIR spectroscopy frequently aids in studies of chemical reactions under a variety of experimental conditions, from high vacuum to aqueous solutions. FTIR spectroscopy can be realized in a multitude of setup geometries sensitive to a small amount of surface adsorbates. Anisotropic film properties can be studied by incorporating polarizing optics in an FTIR setup. FTIR modes of operation discussed in this chapter are Attenuated Total Reflection (ATR), transmission and reflection of the IR radiation through (or from) the sample, Polarization Modulation Infrared Reflection Absorption Spectroscopy (PM-IRRAS) and Infrared Spectroscopic Ellipsometry (IRSE). Practical considerations related to the sample properties (such as doping or roughness) and to the measurement conditions are discussed.

Electrodeposition of Nickel Nanoparticles for the Alkaline Hydrogen Evolution Reaction: Correlating Electrocatalytic Behavior and Chemical Composition

Ni nanoparticles (NPs) consisting of Ni, NiO, and Ni(OH)2 were formed on Ti substrates by electrodeposition as electrocatalysts for the hydrogen evolution reaction (HER) in alkaline solution. Additionally, the deposition parameters including the potential range and the scan rate were varied, and the resulting NPs were investigated by scanning electron microscopy and X-ray photoelectron spectroscopy. The chemical composition of the NPs changed upon using different conditions, and it was found that the catalytic activity increased with an increase in the amount of NiO. From these data, optimized NPs were synthesized; the best sample showed an onset potential of approximately 0 V and an overpotential of 197 mV at a cathodic current density of 10 mA cm-2 as well as a small Tafel slope of 88 mV dec-1 in 1 m KOH, values that are comparable to those of Pt foil. These NPs consist of approximately 25 % Ni and Ni(OH)2 each, as well as approximately 50 % NiO. This implies that to obtain a successful HER electrocatalyst, active sites with differing compositions have to be close to each other to promote the different reaction steps. Long-time measurements (30 h) showed almost complete transformation of the highly active catalyst compound consisting of Ni0 , NiO, and Ni(OH)2 into the less active Ni(OH)2 phase. Nevertheless, the here-employed electrodeposition of nonprecious metal/metal-oxide combination compounds represents a promising alternative to Pt-based electrocatalysts for water reduction to hydrogen.