Christoph Merschjann

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.

Boosting Visible‐Light‐Driven Photocatalytic Hydrogen Evolution with an Integrated Nickel Phosphide–Carbon Nitride System

Solar light harvesting by photocatalytic H2 evolution from water could solve the problem of greenhouse gas emission from fossil fuels with alternative clean energy. However, the development of more efficient and robust catalytic systems remains a great challenge for the technological use on a large scale. Here we report the synthesis of a sol-gel prepared mesoporous graphitic carbon nitride (sg-CN) combined with nickel phosphide (Ni2 P) which acts as a superior co-catalyst for efficient photocatalytic H2 evolution by visible light. This integrated system shows a much higher catalytic activity than the physical mixture of Ni2 P and sg-CN or metallic nickel on sg-CN under similar conditions. Time-resolved photoluminescence and electron paramagnetic resonance (EPR) spectroscopic studies revealed that the enhanced carrier transfer at the Ni2 P-sg-CN heterojunction is the prime source for improved activity.

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.

Complementing Graphenes: 1D Interplanar Charge Transport in Polymeric Graphitic Carbon Nitrides.

Charge transport in polymeric graphitic carbon nitrides is shown to proceed via diffusive hopping of electron and hole polarons with reasonably high mobilities >10(-5) cm(2) V(-1) s(-1). The power-law behavior of the ultrafast luminescence decay exhibits that the predominant transport direction is perpendicular to the graphitic polymer sheets, thus complementing 2D materials like graphene.

Optical nonlinearities of small polarons in lithium niobate

An overview of optical nonlinearities of small bound polarons is given, which can occur in the congruently melting composition of LiNbO3. Such polarons decisively influence the linear and nonlinear optical performance of this material that is important for the field of optics and photonics. On the basis of an elementary phenomenological approach, the localization of carriers in a periodic lattice with intrinsic defects is introduced. It is applied to describe the binding energies of four electron and hole small polarons in LiNbO3: small free NbNb4+ polarons, small bound NbLi4+ polarons, small bound NbLi4+:NbNb4+ bipolarons, and small bound O− hole polarons. For the understanding of their linear interaction with light, an optically induced transfer between nearest-neighboring polaronic sites is assumed. It reveals spectrally well separated optical absorption features in the visible and near-infrared spectral range, their small polaron peak energies and lineshapes. Nonlinear interaction of light is assigned...

Unprecedented Alkylzinc–Magnesium Alkoxide Clusters as Suitable Organometallic Precursors for Magnesium‐Containing ZnO Nanoparticles

The synthesis and characterization of the first heterobimetallic methylzinc-magnesium alkoxide clusters [Me(6)MgZn(6)(OR)(8)] [R=Et (1 a), n-Pr (1 b), nBu (1 c)] with a bis-cubane-shaped MgZn(6)O(8) core is described. The thermal degradation of 1 a-c and mixtures of 1 a and the homometallic MeZn-alkoxide cubane [{MeZnOtBu}(4)] (2) in dry synthetic air led to wide-band-gap semiconducting Mg(x)Zn(1-x)O nanoparticles at temperatures below 500 °C. The final materials were characterized by different analytical techniques such as PXRD, REM, TEM, EDX, and IR spectroscopy. The morphology of the as-prepared magnesium-containing ZnO samples is influenced by the different organo groups (alkoxo) in the precursors. EDX mapping showed that magnesium is uniformly distributed in the ZnO matrix. The incorporation of magnesium led to a distortion of the ZnO lattice with increased a axis and decreased c axis parameters. Room-temperature photoluminescence (PL) spectra reveal that the near-band-edge (NBE) emission of Mg(2+)-doped ZnO is shifted to higher energies relative to that of pure ZnO.

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.

Hologram recording via spatial density modulation of NbLi4+/5+ antisites in lithium niobate

Hologram recording is studied in thermally reduced, nominally undoped lithium niobate in the time domain from 10 ns to 100 s by means of intense ns pump laser pulses (λ = 532 nm) and continuous-wave probe light (λ = 785 nm). It is shown that mixed absorption and phase gratings can be recorded within 8 ns that feature diffraction efficiencies up to 23 % with non-exponential relaxation and lifetimes in the ms-regime. The results are explained comprehensively in the frame of the optical generation of a spatial density modulation of Nb(Li)(4+/5+) antisites and the related optical features, i.e. absorption as well as index changes mutually related via the Kramers-Kronig-relation. Implications of our findings, such as the electrooptical properties of small bound Nb(Li)(4+) polarons, the optical features of Nb(Li)(4+):Nb(Nb)(4+) bipolarons, Nb(Nb)(4+) free polarons and O-hole-polarons, the impact of light polarization of pump and probe beams as well as of the polaron density are discussed.

Small-polaron based holograms in LiNbO3 in the visible spectrum

Diffraction efficiency, relaxation behavior and dependence on pump-beam intensity of small-polaron based holograms are studied in thermally reduced, nominally undoped lithium niobate in the visible spectrum (λ = 488 nm). The pronounced phase gratings with diffraction efficiency up to η = (10.8 ± 1.0)% appeared upon irradiation by single ns-laser pulses (λ = 532 nm) and are comprehensively assigned to the optical formation of spatially modulated densities of small bound NbLi4+ electron polarons, NbLi4+:NbNb4+ electron bipolarons, and O⁻ hole polarons. A remarkable quadratic dependence on the pump-beam intensity is discovered for the recording configuration K || c-axis and can be explained by the electro-optic contribution of the optically generated small bound polarons. We discuss the build-up of local space-charge fields via small-polaron based bulk photovoltaic currents.