This work demonstrates, for the first time, that a variety of disparate and technologically-relevent thermal, mechanical, and electrochemical oxygen-exchange material properties can all be obtained from in situ, current-collector-free wafer curvature measurements.
excellent electromagnetic wave absorption capacity and a localized surface plasmon effect, resulting in broadband light (UVvis-Infrared) absorption and excellent photothermal conversion efficiency. [8][9][10][11][12] Specifically, plasmonic TMN materials have displayed high melting points, excellent thermal and chemical stabilities, and are less expensive than noble metals such as Au. [13] Recently, group 4 TMNs (65% of HfN, 58% of ZrN, and 49% of TiN) exhibited higher photothermal transduction efficiencies than that of commercially Au (43%) samples because of their strong localized surface plasmon resonance effects. [14,15] However, most of these TMN compounds are usually formed from non-or sub-stoichiometric compositions and contain low nitrogen content. [16] Specifically, when the metallic atoms are in higher oxidation states, their corresponding metal nitride compounds are expected to form higher-metal (HM) nitrogen-rich (Nitrogen:Metal ratio >1) nitrides. These characteristics can result in some nitrides, such as HM-Mo 5 N 6 , posessing metallic properties resulting in improved electrocatalytic performance compared to nitrogen-poor nitrides. This can be attributed to the more complicated electron orbital hybridization state in Mo 5 N 6 compared to MoN. [17] For instance, the d band center positions of HM-Mo 5 N 6 and MoN are −1.96 and −2.28 eV. Therefore, the high valence state of Mo atoms in HM-Mo 5 N 6 and strong plasmon effect result in better catalytic activity and demonstrate great potential for solar-driven water generation. Alternatively, other HM nitrides, such as Ta 3 N 5 , demonstrate semiconductivity, which is advantageous for applications such as photoelectrochemical water splitting. [18] Furthermore, due to their higher oxidation states, HM-nitrides exhibit excellent corrosion resistance and high conductivity resulting in electrochemical catalytic behavior under harsh environments such as extremes of pH. [17,19] To date, chemical vapor deposition (CVD) has been explored to synthesize graphene, transition metal dichalcogenides (TMDs) hexagonal boron nitride (h-BN), and has also been used to obtain Mo 2 C, MoN, and Mo 5 N 6 nanosheets through the selection of specific precursors. [20][21][22][23][24][25] Furthermore, other researchers have also obtained metal nitrides via either the salt-template-assisted or atomic substitution methods under an ammonia atmosphere. [26][27][28][29][30] Although there has been Higher-metal (HM) nitrides are a fascinating family of materials being increasingly researched due to their unique physical and chemical properties. However, few focus on investigating their application in a solar steam generation because the controllable and large-scale synthesis of these materials remains a significant challenge. Herein, it is reported that higher-metal molybdenum nitride nanosheets (HM-Mo 5 N 6 ) can be produced at the gramscale using amine-functionalized MoS 2 as precursor. The first-principles calculation confirms amine-functionalized MoS 2 nanosheet effectively lengthens...
Chemical oxygen surface exchange coefficients are used to quantify and rank the performance of oxygen exchange catalysts used in solid oxide fuel cell, solid oxide electrolysis cell, oxygen separation membrane, catalytic converter, and other oxygen-exchange-enabled devices. Unfortunately, during the manufacture and operation of these devices it is easy to introduce siliceous contaminants that degrade their oxygen exchange performance. Surprisingly, despite the well-known negative impact siliceous impurities have on the oxygen transport properties of ceria-based materials, quantitative measurements of how siliceous impurities impact the chemical oxygen surface exchange coefficient of praseodymium doped ceria are largely absent from the literature. In this work, the crystal structure, film thickness, surface composition, bulk composition, and chemical oxygen exchange coefficient of (100)-oriented PCO thin films with, and without, surface silica contaminants were evaluated via X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), X-ray Photoelectron Spectroscopy (XPS), Secondary Ion Mass Spectroscopy (SIMS), and Curvature Relaxation (κR) experiments, respectively. The results show that siliceous surface phases only a few nanometers thick are capable of (1) reducing the PCO chemical oxygen surface exchange coefficient by approximately 3 orders of magnitude and (2) approximately doubling the activation energy for oxygen exchange.
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