Photocatalytic hydrogen production from aqueous solutions over novel Bi0.5Na0.5TiO3 microspheres

Metal oxide compounds containing bismuth are considered as potential candidates for photocatalysis in both contaminant degradation and H₂ generation, due to the interesting lone electron pairs and the band gap narrowing effect of Bi³⁺. Quaternary perovskite oxide Bi_0.5Na_0.5TiO₃ was thus synthesized at low temperature via a soft chemical route. The influence of alkaline concentrations on the structure, morphology, and optical properties of the samples has been systematically investigated. All samples existed as hierarchical microspheres, which are consisted of cubic nanocrystallines. For the first time, the photocatalytic water splitting for H₂ evolution over Bi_0.5Na_0.5TiO₃ has been studied. A high H₂ evolution rate of 325.4 μmol h⁻¹ g cat⁻¹ under the irradiation of a 500 W xenon lamp was obtained. More importantly, no decrease in the catalytic performance was observed after three consecutive runs of 15 h, suggesting new possibility in designing multi-component photocatalysts for future applications.     

Photocatalytic hydrogen evolution over Pt/Cd0.5Zn0.5S from saltwater using glucose as electron donor: An investigation of the influence of electrolyte NaCl

Surface property of Cd_0.5Zn_0.5S in basic aqueous solution was characterized by X-ray photoelectron spectroscope (XPS). The surface S species at Cd_0.5Zn_0.5S under basic condition is substituted by O species. The surface adsorption performance of glucose and NaCl was characterized by adsorption experiment and electrophoretic analysis. Glucose is adsorbed on Cd_0.5Zn_0.5S via two modes. Na⁺ can be also adsorbed on Cd_0.5Zn_0.5S. The effect of electrolyte NaCl on photocatalytic hydrogen evolution over Pt/Cd_0.5Zn_0.5S using glucose as an electron donor has been investigated under visible light irradiation. NaCl can promote markedly the photocatalytic hydrogen evolution, which is very important to practical application. The photocatalytic activity for hydrogen evolution from 3.0 mol L⁻¹ NaCl saltwater increases by 77% compared to that from pure water. A possible mechanism was discussed.     

Electrospun Pt/TiO2 hybrid nanofibers for visible-light-driven H2 evolution

One-dimensional (1D) Pt/TiO₂ hybrid nanofibers (HNFs) with different concentrations of Pt were fabricated by a facile two-step synthesis route combining an electrospinning technique and calcination process. X-ray diffraction (XRD), scanning electron microscopy (SEM), and high-resolution transmission electron microscopy (HRTEM) results showed that the Pt nanoparticles (NPs) with the size of 5–10 nm were well dispersed in the TiO₂ nanofibers (NFs). Further investigations from the UV–Vis diffuse reflectance (DR) and X-ray photoelectron spectroscopy (XPS) analysis revealed that some Pt ions were incorporated into the TiO₂ lattice as Pt⁴⁺ state, which contributed to the visible light absorption of TiO₂ NFs. Meanwhile, the Pt²⁺ ions existing on the surface of Pt NPs resulted in the formation of Pt–O–Ti bond at Pt NPs/TiO₂ NFs interfaces that might serve as an effective channel for improving the charge transfer. The as-electrospun Pt/TiO₂ HNFs exhibited remarkable activities for photocatalytic H₂ evolution under visible light irradiation in the presence of l-ascorbic acid as the sacrificial agent. In particular, the optimal HNFs containing 1.0 at% Pt showed the H₂ evolution rate of 2.91 μmol h⁻¹ and apparent quantum efficiency of 0.04% at 420 nm by using only 5 mg of photocatalysts. The higher photocatalytic activity could be ascribed to the appropriate amount of Pt ions doping and excellent electron-sink effect of Pt NPs co-catalysts.     

Effect of Co doping on the electrochemical properties of Sr2Fe1.5Mo0.5O6 electrode for solid oxide fuel cell

Co is doped to Sr₂Fe_1.5Mo_0.5O₆ to enhance its electrochemical activity as the cathode for intermediate-temperature solid oxide fuel cells. Pure cubic perovskites of Sr₂Fe_1.5−xCo_xMo_0.5O₆ (SF_1.5−xC_xM, x = 0, 0.5, 1) are synthesized using a glycine-nitrate combustion progress. The average thermal expansion coefficient varies from 15.8 to 19.8 × 10⁻⁶ K⁻¹. The electrical conductivity increases while its activation energy decreases with increasing Co content. X-ray photoelectron spectroscopy analysis demonstrates mixed valences of Fe, Co and Mo, suggesting small polaron hopping mechanism. Electrical conductivity relaxation (ECR) measurement shows that the surface exchange coefficient increases about two orders of magnitude when the content increases from x = 0 to x = 1.0, i.e. from 2.55 × 10⁻⁵ to 2.20 × 10⁻³ cm s⁻¹ at 750 °C. ECR also exhibits that chemical diffusion coefficient increases with Co content. Density Functional Theory calculation demonstrates that oxygen vacancy formation energy decreases with Co content, suggesting high oxygen vacancy concentration at high Co content. Impedance spectroscopy on symmetric cells consisting of SF_1.5−xC_xM electrodes and La_0.8Sr_0.2Ga_0.8Mg_0.2O_3−δ electrolytes shows that Co doping is very effective in reducing the interfacial polarization resistance, from 0.105 Ω cm² to 0.056 Ω cm² at 750 °C. These results suggest that Co doping into Sr₂Fe_1.5Mo_0.5O₆ can substantially improve its electrochemical performance.     

In-situ photo-reducing graphene oxide to create Zn0.5Cd0.5S porous nanosheets/RGO composites as highly stable and efficient photoelectrocatalysts for visible-light-driven water splitting

Nanoporous Zn_0.5Cd_0.5S nanosheets/reduced graphene oxide (Zn_0.5Cd_0.5S/RGO) composites were prepared by a facile in-situ photoreduction method of graphene oxide (GO) in the presence of nanoporous Zn_0.5Cd_0.5S single-crystal-like nanosheets under visible light irradiation. The Zn_0.5Cd_0.5S/RGO photoelectrodes was characterized by TEM, IR and Raman spectra. Electrochemical measurements demonstrated that Zn_0.5Cd_0.5S/RGO photoelectrodes own a higher anodic photocurrent density, a lower zero current potential, and a higher photoelectrochemical response than that of pure Zn_0.5Cd_0.5S photoelectrodes under visible light irradiation under the same conditions. This high photochemical activity is predominately ascribed to the presence of RGO, which serves as the electron collector to efficiently prolong the lifetime of photoinduced electrons from the excited Zn_0.5Cd_0.5S nanosheets. In addition, the content of RGO in the composites had a remarkable influence on the photoelectrochemical behaviors of the photoelectrodes and the optimal RGO content was found to be 5 wt%. Zn_0.5Cd_0.5S/RGO composites at RGO content of 5 wt% reached a stable hydrogen production rate of 12.05 μmol h⁻¹ cm⁻² at an externally applied bias of 0.6 V. Furthermore, the Zn_0.5Cd_0.5S/RGO composites as photoelectrodes were found to be highly stable for hydrogen evolution reaction. The electrons stored in RGO are readily discharged or scavenged on demand by the applied positive bias to the counter electrode, and thus rectify the flow of electrons. Importantly, this work may open up a facile in-situ method for using RGO scaffold to create a stable photoelectrode with enhanced photoelectrochemical activities.     

Nanostructured MIEC Ba0.5Sr0.5Co0.6Fe0.4O3−δ (BSCF5564) cathode for IT-SOFC by nitric acid aided EDTA–citric acid complexing process (NECC)

Ba_0.5Sr_0.5Co_0.6Fe_0.4O_3−δ(BSCF5564) was synthesized by nitric acid aided EDTA–citric acid complexing sol-gel method (NECC). Both, the phase formation temperature and time of BSCF5564 synthesized NECC were found to be low i.e. single perovskite phase formation temperature is 200 °C less as compared to the conventional method of synthesis. The orthorhombic perovskite structure has been formed after calcination at 800 °C for 5 h. Scanning electron microscopy reveals the formation of porous material constituting nano-sized and irregularly shaped rod-like structure with particle size approximately ranges from 90 to 160 nm. The total weight loss of the BSCF5564 sample comes out to be 6.6%, indicating that quadrivalence state Co⁴⁺ and Fe⁴⁺ in the sample have been completely reduced to the trivalent state Co³⁺ and Fe³⁺ due to thermal analysis. The value of E_a for BSCF5564 prepared by NECC was 0.2288 eV. The electrical conductivity of BSCF5564 synthesized by NECC is observed to be steady at high temperature (above 700 °C).     

Effects of supersonic treatment on the electrochemical properties and crystal structure of LiMn1.5Ni0.5O4 as a cathode material for Li ion batteries

The electrochemical properties and crystal structure of LiMn_1.5Ni_0.5O₄ treated with supersonic waves in an aqueous Ni-containing solution were investigated by performing charge-discharge tests, inductively coupled plasma (ICP) analysis, scanning electron microscopy (SEM), iodometry, X-ray diffraction (XRD), powder neutron diffraction and synchrotron powder XRD. The charge-discharge curve of LiMn_1.5Ni_0.5O₄ versus Li/Li⁺ has plateaus at 4.1 and 4.7 V. The 4.1 V versus Li/Li⁺ plateau due to the oxidation of Mn^3+/4+ was reduced by the supersonic treatment. During the charge-discharge cycling test at 25 °C, the supersonic treatment increased the discharge capacity of the 50th cycle. Rietveld analysis of the neutron diffraction patterns revealed that the Ni occupancy of the 4b site in LiMn_1.5Mn_0.5O₄, which is mainly occupied by Ni, was increased by the supersonic treatment. This result suggests that Ni²⁺ is partially substituted for Mn^3+/4+ during the supersonic treatment.     

La0.75Sr0.25Cr0.5Mn0.5O3 as hydrogen electrode for solid oxide electrolysis cells

La_0.75Sr_0.25Cr_0.5Mn_0.5O₃ (LSCM) has been applied as hydrogen electrode (cathode) material in solid oxide electrolysis cells operating with different steam concentrations (20, 40, 60 and 80 vol.% absolute humidity (AH)) using 40 sccm H₂ carrier gas at 800, 850 and 900 °C, respectively. Impedance spectra and voltage-current curves were measured as a function of cell electrolysis current density and steam concentration to characterize the cell performance. The cell resistance decreased with the increase in electrolysis current density while increased with the increase in steam concentration under the same electrolysis current density. At 1.6 V applied electrolysis voltage, the maximum consumed current density increased from 431 mA cm⁻² for 20 vol.% AH to 593 mA cm⁻² for 80 vol.% AH at 850 °C. Polarization and impedance spectra experiments revealed that LSCM-YSZ hydrogen electrode played a major role in the electrolysis reaction.     

Effect of equivalent and non-equivalent Al substitutions on the structure and electrochemical properties of LiNi0.5Mn0.5O2

Pristine, equivalently and non-equivalently Al substituted LiNi_0.5Mn_0.5O₂ materials were prepared by a combination of co-precipitation and solid-state reaction. As shown by XRD and XPS, lattice volume shrinkage of LiNi_0.5(Mn_0.45Al_0.05)O₂ was attributed to the presence of Ni in both 2+ and 3+, while the lattice volume expansion of Li(Ni_0.45Al_0.05)Mn_0.5O₂ was caused by lowering the average oxidation state of Mn. Electrochemical performance of LiNi_0.5Mn_0.5O₂ materials can be greatly affected by the change of oxidation states of the transition metals by Al substitution. Non-equivalent substitution of Al for Ni leads to deteriorated discharge performance and cyclic stability due to the reduction of the electrochemical active Ni²⁺ and structure supported Mn⁴⁺, while an increase in the amount of Ni²⁺ in LiNi_0.5(Mn_0.45Al_0.05)O₂ brings obvious improvement of the electrochemical properties. EIS analyses of the electrode materials at pristine and charged states indicate that the poor electrochemical performance of Li(Ni_0.45Al_0.05)Mn_0.5O₂ material can be ascribed to the higher charge transfer resistance and surface film resistance, and the observed higher current rate capability of LiNi_0.5(Mn_0.45Al_0.05)O₂ can be understood due to the better charge transfer kinetics.     

Electrochemical study of Ba0.5Sr0.5Co0.8Fe0.2O3 perovskite as bifunctional catalyst in alkaline media

Ba_0.5Sr_0.5Co_0.8Fe_0.2O₃ perovskite oxide has been synthesized by a sol–gel method, and characterized by XRD, SEM, BET. This oxide has a porous structure and a specific surface area of 2.78 m² g⁻¹. The catalytic activity of the oxide for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) in 0.1 M KOH solution has been studied by using a rotating ring-disk electrode (RRDE) technique. RRDE results show that the ORR mainly favors a direct four electron pathway, and a maximum cathodic current density of 6.25 mA cm⁻² at 2500 rpm was obtained, which is close to the behavior of Pt/C (20 wt% Pt on carbon) electrocatalyst in the same testing conditions. Compared with pure C electrode, BSCF is more active for OER, a lower onset potential for OER and a bigger anodic current at the same applied potential are observed.     

PrBa0.5Sr0.5Co2O5+x as cathode material based on LSGM and GDC electrolyte for intermediate-temperature solid oxide fuel cells

PrBa_0.5Sr_0.5Co₂O_5+x (PBSC) oxides have been evaluated as cathode materials for intermediate-temperature solid oxide fuel cells (IT-SOFCs) with Ce_0.9Gd_0.1O_1.95 (GDC) and La_0.9Sr_0.1Ga_0.8Mg_0.2O_3−δ (LSGM) as electrolytes. XRD results show that PBSC cathode is chemically compatible with the intermediate-temperature electrolyte materials GDC and LSGM. The maximum electrical conductivity is 1522 S cm⁻¹ at 100 °C and its value is higher than 581 S cm⁻¹ over the whole temperature range investigated. Microstructures show that the contact between PBSC and LSGM is better than that between PBSC and GDC. The area-specific resistances (ASRs) of PBSC cathode on GDC and LSGM electrolytes are 0.048 and 0.027 Ωcm² at 800 °C, respectively. The electrolyte-supported (thickness of electrolyte is 300 μm) fuel cells generate good performance with the maximum power densities of 617 mW cm⁻² on GDC electrolyte and 1021 mW cm⁻² on LSGM electrolyte at 800 °C. All results demonstrate that PBSC oxide is a very promising cathode material for application in IT-SOFCs and this cathode based on LSGM electrolyte obtained better performance than on GDC electrolyte.     

In-situ XRD investigations on structure changes of ZrO2-coated LiMn0.5Ni0.5O2 cathode materials during charge

The structural changes of pristine and ZrO₂-coated LiMn_0.5Ni_0.5O₂ cathode materials were investigated by using in situ X-ray diffraction (XRD) during charging process. An obviously solid solution phase transition from a hexagonal structure (H1) to another hexagonal structure (H2) was observed during the charging process at a constant current of 0.3 mA in the potential range of 2.5–5.7 V. The second hexagonal structure has a shorter a-axis and a longer c-axis before the crystal collapse. Before the structure collapses the c-axis length increases to maximum and then significantly decreases to 14.1 Å. The c-axis length of the pristine and ZrO₂-coated LiMn_0.5Ni_0.5O₂ increases to the maximum at the charge capacity of 119.2 and 180.9 mAh g⁻¹, respectively. It can be concluded that the ZrO₂ coating can strongly stabilize the crystal structure of the LiMn_0.5Ni_0.5O₂ compound from the comparison of the lattice parameter variations between the pristine and the ZrO₂-coated LiMn_0.5Ni_0.5O₂ compounds upon charge. The potential fluctuation resulting from the decomposition of electrolytes starts at the charge capacity of around 200 and 260 mAh g⁻¹ for the pristine and ZrO₂-coated LiMn_0.5Ni_0.5O₂, respectively. It suggests that the ZrO₂ coating layer can impede the reaction between the cathode material and electrolyte.     

An efficient ZnS-UV photocatalysts generated in situ from ZnS(en)0.5 hybrid during the H2 production in methanol–water solution

Highly active ZnS-UV was obtained in situ from ZnS(en)_0.5 hybrid during the hydrogen formation using a methanol–water solution under UV irradiation. X-ray diffraction patterns and UV spectroscopy for both ZnS-UV and ZnS-400 obtained from the calcination of the ZnS(en)_0.5 hybrid showed similar structural and photophysical properties; however, the efficiency of the ZnS-UV semiconductor was 7 times higher (4825 μmol h⁻¹ g⁻¹) compared to the ZnS-400. The highest H₂ production was obtained using a UV lamp of very low intensity (2.2 mW cm⁻¹) and it is attributed to a quantum size effect caused by the slow elimination of ethylenediamine (en) in the structural ZnS layer during the UV irradiation.     

Stable, easily sintered BaCe0.5Zr0.3Y0.16Zn0.04O3−δ electrolyte-based protonic ceramic membrane fuel cells with Ba0.5Sr0.5Zn0.2Fe0.8O3−δ perovskite cathode

A stable, easily sintered perovskite oxide BaCe_0.5Zr_0.3Y_0.16Zn_0.04O_3−δ (BCZYZn) as an electrolyte for protonic ceramic membrane fuel cells (PCMFCs) with Ba_0.5Sr_0.5Zn_0.2Fe_0.8O_3−δ (BSZF) perovskite cathode was investigated. The BCZYZn perovskite electrolyte synthesized by a modified Pechini method exhibited higher sinterability and reached 97.4% relative density at 1200 °C for 5 h in air, which is about 200 °C lower than that without Zn dopant. By fabricating thin membrane BCZYZn electrolyte (about 30 μm in thickness) on NiO–BCZYZn anode support, PCMFCs were assembled and tested by selecting stable BSZF perovskite cathode. An open-circuit potential of 1.00 V, a maximum power density of 236 mW cm⁻², and a low polarization resistance of the electrodes of 0.17 Ω cm² were achieved at 700 °C. This investigation indicated that proton conducting electrolyte BCZYZn with BSZF perovskite cathode is a promising material system for the next generation solid oxide fuel cells.     

Solution combustion synthesis of layered LiNi0.5Mn0.5O2 and its characterization as cathode material for lithium-ion cells

LiNi_0.5Mn_0.5O₂, a promising cathode material for lithium-ion batteries, is synthesized by a novel solution-combustion procedure using acenaphthene as a fuel. The powder X-ray diffraction (XRD) pattern of the product shows a hexagonal cell with a = 2.8955 Å and c = 14.1484 Å. Electron microscopy investigations indicate that the particles are of sub-micrometer size. The product delivers an initial discharge capacity of 161 mAh g⁻¹ between 2.5 and 4.6 V at a 0.1 C rate and could be subjected to more than 50 cycles. The electrochemical activity is corroborated with cyclic voltammetric (CV) and electrochemical impedance data. The preparative procedure presents advantages such as a low cation mixing, sub-micron particles and phase purity.     

Phase stability of Sm0.5Sr0.5CoO3 cathodes for on-planar type, single-chamber, solid oxide fuel cells

The stability of Sm_0.5Sr_0.5CoO₃ (SSC) under reduction conditions is investigated to determine whether it can be used as a cathode material in on-planar type, single-chamber, solid oxide fuel cells. The techniques of X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy are used to reveal the reduction mechanism of SSC. Impedance spectroscopy analysis also provides a better understanding of the influence of decomposed SSC phases on cathode performance. Decomposition of SSC occurs on the surface by the formation of dot-shaped SrO, Co(OH)₂ and CoO on top of the reduced SSC layer at 250 °C in 4% H₂O-96% H₂. The SSC perovskite structure is destroyed at 350 °C in pure hydrogen. There is a catastrophic microstructural change in which SSC is completely decomposed to SrO and CoO that cover the surface of Sm₂O₃.     

Evaluation of nano-structured Ir0.5Mn0.5O2 as a potential cathode for intermediate temperature solid oxide fuel cell

A novel Ir_0.5Mn_0.5O₂ cathode has been synthesized by thermal decomposition of mixed H₂IrCl₆ and Mn(NO₃)₂ water solution. The Ir_0.5Mn_0.5O₂ cathode has been characterized by XRD, field emission SEM (FESEM) and AC impedance spectroscopy. XRD result shows that rutile-structured Ir_0.5Mn_0.5O₂ phase is formed by thermal decomposition of mixed H₂IrCl₆ and Mn(NO₃)₂ water solution. FESEM micrographs show that a porous structure with well-necked particles forms in the cathode after sintering at 1000 °C. The average grain size is between 20 and 30 nm. Two depressed arcs appear in the medium-frequency and low-frequency region, indicating that there are at least two different processes in the cathode reaction: charge transfer and molecular oxygen dissociation followed by surface diffusion. The minimum area specific resistance (ASR) is 0.67 Ω cm² at 800 °C. The activation energy for the total oxygen reduction reaction is 93.7 kJ mol⁻¹. The maximum power densities of the Ir_0.5Mn_0.5O₂/LSGM/Pt cell are 43.2 and 80.7 mW cm⁻² at 600 and 700 °C, respectively.     

Enhanced performance of solid oxide fuel cells with Ni/CeO2 modified La0.75Sr0.25Cr0.5Mn0.5O3−δ anodes

The optimization of electrodes for solid oxide fuel cells (SOFCs) has been achieved via a wet impregnation method. Pure La_0.75Sr_0.25Cr_0.5Mn_0.5O_3−δ (LSCrM) anodes are modified using Ni(NO₃)₂ and/or Ce(NO₃)₃/(Sm,Ce)(NO₃)_x solution. Several yttria-stabilized zirconia (YSZ) electrolyte-supported fuel cells are tested to clarify the contribution of Ni and/or CeO₂ to the cell performance. For the cell using pure-LSCrM anodes, the maximum power density (P_max) at 850 °C is 198 mW cm⁻² when dry H₂ and air are used as the fuel and oxidant, respectively. When H₂ is changed to CH₄, the value of P_max is 32 mW cm⁻². After 8.9 wt.% Ni and 5.8 wt.% CeO₂ are introduced into the LSCrM anode, the cell exhibits increased values of P_max 432, 681, 948 and 1135 mW cm⁻² at 700, 750, 800 and 850 °C, respectively, with dry H₂ as fuel and air as oxidant. When O₂ at 50 mL min⁻¹ is used as the oxidant, the value of P_max increases to 1450 mW cm⁻² at 850 °C. When dry CH₄ is used as fuel and air as oxidant, the values of P_max reach 95, 197, 421 and 645 mW cm⁻² at 750, 800, 850 and 900 °C, respectively. The introduction of Ni greatly improves the performance of the LSCrM anode but does not cause any carbon deposit.