Comparison of a solid oxide cell with nickel/gadolinium‐doped ceria fuel electrode during operation with hydrogen/steam and carbon monoxide/carbon dioxide

Solid oxide cells (SOCs) offer the possibility to operate on hydrogen/steam (H$_2$/H$_2$O), carbon monoxide/carbon dioxide (CO/CO$_2$), and mixtures thereof in the fuel cell as well as in the electrolyzer mode. In this study, the electrochemical processes in an electrolyte-supported SOC exhibiting a La$_w$ Sr$_x$ Co$_y$ Fe$_z$ O$_{(3-δ)}$ air electrode and a nickel/gadolinium-doped ceria (Ni/CGO) fuel electrode (FE) were analyzed by electrochemical impedance spectroscopy, and the subsequent impedance data analysis by the distribution of relaxation times for CO/CO$_2$ fuel mixtures. A physicochemical equivalent circuit model was fitted to the measured spectra. With the help of the extracted parameters, a zero-dimensional direct current cell model was parametrized to simulate the current-voltage behavior of the cell. This approach, previously implemented for H$_2$/H$_2$O fuel mixtures, is extended toward CO/CO$_2$ fuels. It will be shown that the same model – with adapted parameters for the FE – can be applied. A comparison of measured and simulated current-voltage curves showed an excellent agreement for both fuels and operating modes (solid oxide fuel cell/solid oxide electrolyzer cell). Simulations reveal that there is nearly no performance difference between H$_2$O and CO$_2$ electrolysis for the electrolyte-supported cell with Ni/CGO FE in comparison to an anode-supported cell with Ni/yttria-stabilized zirconia FE

Wafer-sized multifunctional polyimine-based two-dimensional conjugated polymers with high mechanical stiffness

One of the key challenges in two-dimensional (2D) materials is to go beyond graphene, a prototype 2D polymer (2DP), and to synthesize its organic analogues with structural control at the atomic- or molecular-level. Here we show the successful preparation of porphyrin-containing monolayer and multilayer 2DPs through Schiff-base polycondensation reaction at an air-water and liquid-liquid interface, respectively. Both the monolayer and multilayer 2DPs have crystalline structures as indicated by selected area electron diffraction. The monolayer 2DP has a thickness of∼0.7 nm with a lateral size of 4-inch wafer, and it has a Young's modulus of 267±30 GPa. Notably, the monolayer 2DP functions as an active semiconducting layer in a thin film transistor, while the multilayer 2DP from cobalt-porphyrin monomer efficiently catalyses hydrogen generation from water. This work presents an advance in the synthesis of novel 2D materials for electronics and energy-related applications

1D p–n Junction Electronic and Optoelectronic Devices from Transition Metal Dichalcogenide Lateral Heterostructures Grown by One-Pot Chemical Vapor Deposition Synthesis

Lateral heterostructures of dissimilar monolayer transition metal dichalcogenides provide great opportunities to build 1D in-plane p–n junctions for sub-nanometer thin low-power electronic, optoelectronic, optical, and sensing devices. Electronic and optoelectronic applications of such p–n junction devices fabricated using a scalable one-pot chemical vapor deposition process yielding MoSe2-WSe2 lateral heterostructures are reported here. The growth of the monolayer lateral heterostructures is achieved by in situ controlling the partial pressures of the oxide precursors by a two-step heating protocol. The grown lateral heterostructures are characterized structurally and optically using optical microscopy, Raman spectroscopy/microscopy, and photoluminescence spectroscopy/microscopy. High-resolution transmission electron microscopy further confirms the high-quality 1D boundary between MoSe2 and WSe2 in the lateral heterostructure. p–n junction devices are fabricated from these lateral heterostructures and their applicability as rectifiers, solar cells, self-powered photovoltaic photodetectors, ambipolar transistors, and electroluminescent light emitters are demonstrated. © 2021 The Authors. Advanced Functional Materials published by Wiley-VCH Gmb

A Study in Red: The Overlooked Role of Azo‐Moieties in Polymeric Carbon Nitride Photocatalysts with Strongly Extended Optical Absorption

The unique optical and photoredox properties of heptazine-based polymeric carbon nitride (PCN) materials make them promising semiconductors for driving various productive photocatalytic conversions. However, their typical absorption onset at ca. 430–450 nm is still far from optimum for efficient sunlight harvesting. Despite many reports of successful attempts to extend the light absorption range of PCNs, the determination of the structural features responsible for the red shift of the light absorption edge beyond 450 nm has often been obstructed by the highly disordered structure of PCNs and/or low content of the moieties responsible for changes in optical and electronic properties. In this work, we implement a high-temperature (900 °C) treatment procedure for turning the conventional melamine-derived yellow PCN into a red carbon nitride. This approach preserves the typical PCN structure but incorporates a new functionality that promotes visible light absorption. A detailed characterization of the prepared material reveals that partial heptazine fragmentation accompanied by de-ammonification leads to the formation of azo-groups in the red PCN, a chromophore moiety whose role in shifting the optical absorption edge of PCNs has been overlooked so far. These azo moieties can be activated under visible-light (470 nm) for H₂ evolution even without any additional co-catalyst, but are also responsible for enhanced charge-trapping and radiative recombination, as shown by spectroscopic studies

Exciton spectroscopy and unidirectional transport in MoSe2-WSe2 lateral heterostructures encapsulated in hexagonal boron nitride

Chemical vapor deposition (CVD) allows lateral edge epitaxy of transition metal dichalcogenide heterostructures. Critical for carrier and exciton transport is the material quality and the nature of the lateral heterojunction. Important details of the optical properties were inaccessible in as-grown heterostructure samples due to large inhomogeneous broadening of the optical transitions. Here we perform optical spectroscopy of CVD grown MoSe$_2$-WSe$_2$ lateral heterostructures, encapsulated in hBN. Photoluminescence (PL), reflectance contrast and Raman spectroscopy reveal optical transition linewidths similar to high quality exfoliated monolayers, while PL imaging experiments uncover the effective excitonic diffusion length of both materials. The typical extent of the covalently bonded MoSe$_2$-WSe$_2$ heterojunctions is 3 nm measured by scanning transmission electron microscopy (STEM). Tip-enhanced, sub-wavelength optical spectroscopy mapping shows the high quality of the heterojunction which acts as an excitonic diode resulting in unidirectional exciton transfer from WSe$_2$ to MoSe$_2$

Atomic Scale Microstructure and Properties of Se-Deficient Two-Dimensional MoSe2

We study the atomic scale microstructure of non-stoichiometric two-dimensional(2D) transition metal dichalcogenide MoSe2-x, by employing aberration-corrected high-resolution transmission electron microscopy. We show that a Se-deficit in single layers of MoSe2 grown by molecular beam epitaxy gives rise to a dense network of mirror-twin-boundaries (MTBs) decorating the 2D-grains. With the use of density functional theory calculations, we further demonstrate that MTBs are thermodynamically stable structures in Se-deficient sheets. These line defects host spatially localized states with energies close to the valence band minimum, thus giving rise to enhanced conductance along straight MTBs. However, electronic transport calculations show that-the transmission of hole charge carriers across MTBs is strongly suppressed due to band bending effects. We further observe formation of MTBs during in situ removal of Se atoms by the electron beam of the microscope, thus confirming that MTBs appear due-to Se-deficit, and not coalescence of individual grains during growth. At a very high local Se-deficit, the 2D sheet becomes unstable and transforms to a nanowire. Our results on Se-deficient MoSe2 suggest routes toward engineering the properties of 2D transition Metal dichalcogenides by deviations from the stoichiometric composition

1D <i>p–n</i> Junction Electronic and Optoelectronic Devices from Transition Metal Dichalcogenide Lateral Heterostructures Grown by One‐Pot Chemical Vapor Deposition Synthesis

Funder: European Union's Horizon 2020Funder: Ministry of Science, Research and the ArtsFunder: Max Planck School of PhotonicsFunder: European Union; Id: http://dx.doi.org/10.13039/501100000780Funder: European Social FundsAbstract: Lateral heterostructures of dissimilar monolayer transition metal dichalcogenides provide great opportunities to build 1D in‐plane p–n junctions for sub‐nanometer thin low‐power electronic, optoelectronic, optical, and sensing devices. Electronic and optoelectronic applications of such p–n junction devices fabricated using a scalable one‐pot chemical vapor deposition process yielding MoSe2‐WSe2 lateral heterostructures are reported here. The growth of the monolayer lateral heterostructures is achieved by in situ controlling the partial pressures of the oxide precursors by a two‐step heating protocol. The grown lateral heterostructures are characterized structurally and optically using optical microscopy, Raman spectroscopy/microscopy, and photoluminescence spectroscopy/microscopy. High‐resolution transmission electron microscopy further confirms the high‐quality 1D boundary between MoSe2 and WSe2 in the lateral heterostructure. p–n junction devices are fabricated from these lateral heterostructures and their applicability as rectifiers, solar cells, self‐powered photovoltaic photodetectors, ambipolar transistors, and electroluminescent light emitters are demonstrated