Plasmonic semiconductor: A tunable non-metal photocatalyst

Doped semiconductor, a newly discovered plasmonic nanomaterial, has attracted tremendous interest due to its tunable properties. In the field of photocatalysis, the perfect combination of metal-like and semiconductor properties makes it the replacement and supplement of metal plasmonic nanomaterials. This new plasmonic photocatalysis offers high conversion efficiencies and wide optical absorption range with low fabrication costs. This article reviews the recent developments and achievements by which the localized surface plasmon resonance (LSPR) in non-metal plasmonic nanomaterial for photocatalytic applications, including pure non-metal plasmonic photocatalysts and various enhancement strategies such as doping, co-catalyst, heterojunction, LSPR coupling and upconversion luminescence enhancement. It broadens the horizons for plasmonics in the study of photocatalysis and even in energy-related applications.     

A PBI‐Sb0.2Sn0.8P2O7‐H3PO4 Composite Membrane for Intermediate Temperature Fuel Cells

Fine particles of a solid proton conductor Sb_0.2Sn_0.8P₂O₇ were incorporated in PBI‐H₃PO₄ membranes with 20 wt.%. In SEM figures, the Sb_0.2Sn_0.8P₂O₇ particles exhibited even and uniform distribution in the PBI‐Sb_0.2Sn_0.8P₂O₇ membrane. Influences of the immersing time and the concentration of H₃PO₄ solution for immersion on H₃PO₄ loading level were investigated. H₃PO₄ loading level was found an important factor on membrane conductivity. Incorporation of Sb_0.2Sn_0.8P₂O₇ in the PBI‐H₃PO₄ membrane resulted in greater membrane conductivities. In the single cell tests, the peak power density of the membrane electrode assembly (MEA) with the PBI‐Sb_0.2Sn_0.8P₂O₇‐H₃PO₄ membrane was also greater than that of a MEA with PBI‐H₃PO₄ membrane. One MEA using PBI‐Sb_0.2Sn_0.8P₂O₇‐H₃PO₄ membrane achieved a peak power density of 0.67 W cm^–2 at 175 °C with H₂/O₂ and exhibited satisfactory stability.     

A photoelectrochemical investigation of the hydrogen-evolving doped TiO2 nanotube arrays electrode

The present work investigates the photoelectrochemical behavior of nanotubular N/C-TiO₂ electrode for hydrogen production. Via the sonoelectrochemical anodization process of 1 h, N-containing TiO₂ based nanotube arrays(N-TNT) with the length of about 650 nm were fabricated in fluoride aqueous solution added 0.25 M NH₄NO₃; C-containing TiO₂ based nanotube arrays(C-TNT) with the length of about 2 μm were prepared in fluoride ethylene glycol solution. In virtue of the longer tubes with the larger surface areas, C-TNT can harvest more light and produce more photoactive sites than N-TNT, which also made the charge transfer resistance in C-TNT larger than that in N-TNT. Considered the more negative flat band potential of C-TNT, C-TNT has the smaller energy barrier and the better photoelectrochemical activity. It may be attributed to the appropriate defect concentration gradient owing to the modification of C element. Under UV-vis light (320-780 nm) irradiation, the average hydrogen generation rate of C-TNT was 282 μL h⁻¹ cm⁻². The surface properties and near-surface properties of the resultant electrode were synthetically analyzed by using UV-vis diffuse reflectance spectra(DRS), field emission scanning electron microscopy (FESEM), I-t curves, and electrochemical impedance spectroscopy (EIS) techniques.     

Microstructure developments of F-doped SiO2 thin films prepared by liquid phase deposition

This study presents a systematic investigation of the microstructure dependence of liquid phase deposition (LPD) of SiO₂ films on solution parameters and deposition temperature. The corresponding deposition rate and film roughness were also evaluated under various deposition conditions. Smooth and sufficiently dense SiO₂ films, which are the prerequisite for reliable low-k dielectric applications, were deposited on both silicon and fluorine-doped tin oxide coated glass substrates from supersaturated hydrofluorosilicic acid (H₂SiF₆) solution with the addition of boric acid (H₃BO₃). It is shown that H₂SiF₆ acid controls the surface morphology and grain structure through surface reaction while H₃BO₃ acid prompts bulk precipitation in solution. For the 208-nm thick SiO₂ film, the breakdown field exceeded 1.9 MV/cm and the leakage current density was on the order of 10^− 9 A/cm² at 4 V, indicating excellent insulating properties of LPD SiO₂ films. The strong presence of Si-O-Si and some Si-F with little Si-OH bond as shown in FT-IR spectra indicate that the LPD SiO₂ films have mostly a silica network with some fluorine (F) content. F-doping was self-incorporated into the silica films from the H₂SiF₆ solution during deposition process.     

Electrochemical characteristics of samaria-doped ceria infiltrated strontium-doped LaMnO3 cathodes with varied thickness for yttria-stabilized zirconia electrolytes

Samaria-doped ceria (SDC) infiltrated into strontium-doped LaMnO₃ (LSM) cathodes with varied cathode thickness on yttria-stabilized zirconia (YSZ) were investigated via symmetrical cell, half cell, and full cell configurations. The results of the symmetrical cells showed that the interfacial polarization resistance (R_P) decreased with increasing electrode thickness up to ∼30 μm, and further increases in the thickness of the cathode did not cause significant variation of electrode performance. At 800 °C, the minimum R_P was around 0.05 Ω cm². The impedance spectra indicated that three main electrochemical processes existed, possibly corresponding to the oxygen ion incorporation, surface diffusion of oxygen species and oxygen adsorption and dissociation. The DC polarization on the half cells and characterization of the full cells also demonstrated a similar correlation between the electrode performance and the electrode thickness. The peak power densities of the single cells with the 10, 30, and 50-μm thick electrodes were 0.63, 1.16 and 1.11 W cm⁻², respectively. The exchange current densities under moderate polarization are calculated and possible rate-determining steps are discussed.     

Sm0.2(Ce1−xTix)0.8O1.9 modified Ni-yttria-stabilized zirconia anode for direct methane fuel cell

Sm_0.2(Ce_1−xTi_x)_0.8O_1.9 (SCTx, x = 0-0.29) modified Ni-yttria-stabilized zirconia (YSZ) has been fabricated and evaluated as anode in solid oxide fuel cells for direct utilization of methane fuel. It has been found that both the amount of Ti-doping and the SCTx loading level in the anode have substantial effect on the electrochemical activity for methane oxidation. Optimal anode performance for methane oxidation has been obtained for Sm_0.2(Ce_0.83Ti_0.17)_0.8O_1.9 (SCT0.17) modified Ni-YSZ anode with SCT0.17 loading of about 241 mg cm⁻² resulted from four repeated impregnation cycles. When operating on humidified methane as fuel and ambient air as oxidant at 700 °C, single cells with the configuration of SCT0.17 modified Ni-YSZ anode, YSZ electrolyte and La_0.6Sr_0.4Co_0.2Fe_0.8O₃-Sm_0.2Ce_0.8O_1.9 (LSCF-SDC) composite cathode show the polarization cell resistance of 0.63 Ω cm² under open circuit conditions and produce a peak power density of 383 mW cm⁻². It has been revealed that the coated Ti-doped SDC on Ni-YSZ anode not only effectively prevents the methane fuel from directly impacting on the Ni particles, but also enhances the kinetics of methane oxidation due to an improved oxygen storage capacity (OSC) and redox equilibrium of the anode surface, resulting in significant enhancement of the SCTx modified Ni-YSZ anode for direct methane oxidation.     

Y-doped BaCeO3−δ nanopowders as proton-conducting electrolyte materials for ethane fuel cells to co-generate ethylene and electricity

Y-doped BaCeO_3−δ (BCY) powders synthesized using a combustion method are pure perovskite phases. The particles are uniform spherical particles about 50 nm. The properties of BCY proton-conducting electrolyte sintered at different temperatures from pressed nanopowders were systematically investigated. Dense BCY pellets are obtained at temperatures higher than 1400 °C for 10 h. Electrical conductivity and resistance to CO₂ atmosphere each increase with sintering temperature. Fuel cells having about 0.8 mm thick BCY electrolyte and Pt electrodes co-produce 151 mW cm⁻² electrical power and value-added ethylene with selectivity over 90% at ethane conversion about 35% at 700 °C.     

High performance electrolyte-coated anodes for low-temperature solid oxide fuel cells: Model and Experiments

A geometric micro-model and experiment development are presented for electrolyte-coated anodes with high performance in solid oxide fuel cells. The anodes are based on electron conducting frameworks, where fine, oxygen-ion conducting inclusions are introduced via an ion impregnation process. The model shows that the length of triple-phase-boundary (TPB) increases with the loading of the coated electrolyte, and is dependent only on the loading before a maximum loading for monolayer coverage is obtained. The maximum loading increases with the porosity of the framework. As a result, the prolonged TPB length can be achieved by increasing the porosity and the loading. In the experimental study, Ni was used as the electron conductor, and samaria-doped ceria (SDC) was employed as the electrolyte to form anode-supported single cells. The cell performance was evaluated using humidified hydrogen as the fuel. The peak power density increased with SDC loading to a maximum value and decreased when the loading was further increased. The highest peak power density of the cells whose anodes were prepared with 10, 20 and 30 wt.% pore former was 571, 631 and 723 mW cm⁻², corresponding to 508, 564 and 648 mg cm⁻³ of SDC loading, respectively. The experimental results are in good agreement with the model prediction. Therefore, this work demonstrates theoretically and experimentally that optimization of the porosity and electrolyte loading is critical for further improving the performance of electrolyte-coated anodes.     

A high performance direct ammonia fuel cell using a mixed ionic and electronic conducting anode

A high performance direct ammonia fuel cell incorporating a doubly doped barium cerate electrolyte and a novel cermet anode consisting of europium doped barium cerate, a mixed ionic and electronic solid electrolyte, and Ni was studied. The catalytic activity of the cermet anodes was superior to that of Pt catalysts. The I–V and power density data suggest that the direct ammonia fuel cell could be operated at temperatures as low as 450 °C. The fuel cell was operated with ammonia as fuel in excess of 500 h without significant deterioration in performance.     

Novel cobalt-free cathode materials BaCexFe1−xO3−δ for proton-conducting solid oxide fuel cells

A series of cobalt-free and low cost BaCe_xFe_1−xO_3−δ (x = 0.15, 0.50, 0.85) materials are successful synthesized and used as the cathode materials for proton-conducting solid oxide fuel cells (SOFCs). The single cell, consisting of a BaZr_0.1Ce_0.7Y_0.2O_3−δ (BZCY7)-NiO anode substrate, a BZCY7 anode functional layer, a BZCY7 electrolyte membrane and a BaCe_xFe_1−xO_3−δ cathode layer, is assembled and tested from 600 to 700 °C with humidified hydrogen (3% H₂O) as the fuel and the static air as the oxidant. Within all the cathode materials above, the cathode BaCe_0.5Fe_0.5O_3−δ shows the highest cell performance which could obtain an open-circuit potential of 0.99 V and a maximum power density of 395 mW cm⁻² at 700 °C. The results indicate that the Fe-doped barium cerates can be promising cathodes for proton-conducting SOFCs.