Directed electrochemical synthesis of ZnO/PDMcT core/shell nanorod arrays with enhanced photoelectrochemical properties

In this paper, we demonstrate a simple two-step electrochemical deposition strategy for synthesizing ZnO/Poly(2,5-dimercapto-1,3,4-thiadiazole) (PDMcT) core/shell nanorod arrays. The as-synthesized ZnO/PDMcT samples are characterized by Fourier-transform infrared (FTIR), Raman spectroscopy, power X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The ZnO/PDMcT nanorod arrays are found to exhibit significantly enhanced photocurrent density in photoelectrochemical cell applications as compared to the prinstine ZnO nanorod arrays.     

Deposition of heterojunction of ZnO on hydrogenated TiO2 nanotube arrays by atomic layer deposition for enhanced photoelectrochemical water splitting

The heterojunction of ZnO was deposited on hydrogenated TiO₂ nanotube arrays (H–TiO₂) by atomic layer deposition (ALD) with various cycles. The ZnO was uniformly wrapped with the H–TiO₂ samples and the thickness could be accurately controlled by the cycle numbers of ALD. The higher growth rate ~2.7 Å/cycle was obtained due to the surface amorphous layer, compared with the air-treated samples (A-TiO₂), ~2.3 Å/cycle. When the cycle numbers increased to 200, nanowire arrays appeared. Interestingly, the absorption in the visible light region improved more significantly when ALD ZnO was employed for the H–TiO₂ rather than the A-TiO₂ samples. The H–TiO₂ samples with 42 nm of ALD ZnO exhibited enhanced photoelectrochemical water splitting performances, compared with the A-TiO₂ with 42 nm of ALD ZnO. This was related to the higher degree of the electronic band bending and improved photo-response in the UV and visible light region, resulting from the oxygen vacancies.     

Fabrication of In2O3/In2S3 heterostructures for enhanced photoelectrochemical performance

Constructing core/shell heterojunction has always been an effective strategy for photoelectrochemical (PEC) water splitting owing to special morphology characterization and band structure. Herein, we synthesized a series of In₂O₃/In₂S₃ core/shell structure photoanodes via a simple two-step hydrothermal method to improve the PEC performance of In₂O₃. Various methods were employed to investigate the influence of sulfurization time on the morphologies, microstructures, photoelectrochemical properties and band structures of the as-prepared photoanodes. The results indicated that the In₂O₃/In₂S₃-5 possessed stronger visible light absorption, faster charge transfer rate and higher electron carrier density, which resulted in an excellent PEC performance. Under visible light irradiation, the photocurrent density of the In₂O₃/In₂S₃-5 photoanode reached 0.53 mA cm⁻² at 1.23 V vs RHE in 1 M NaOH solution, which was about twice as high as that of the pristine In₂O₃. Furthermore, the onset potential of the In₂O₃/In₂S₃-5 photoanode had an obvious negative shift (~200 mV) when compared to the pure In₂O₃ nanorod photoanode.     

Fabrication of NiO/Ta2O5 composite photocatalyst for hydrogen production under visible light

A series of novel composite photocatalysts, NiO/Ta₂O₅, were synthesized by the solid‐state reaction and successfully characterized by X‐ray diffraction, Transmission electron microscopy, diffused reflectance ultraviolet and visible (DRUV‐vis) spectroscopy, Photoluminescence and X‐ray photoelectron spectroscopy. Powder X‐ray diffraction (PXRD) pattern indicated the formation of composite material. The red shift in the absorption edges of the newly prepared composite photocatalysts were well observed from the DRUV‐vis spectra. The composite photocatalyst prepared at metal ratio (1:3) showed highest result toward hydrogen production under ultraviolet and visible light irradiation in the presence of methanol as a sacrificial agent. Copyright © 2011 John Wiley & Sons, Ltd.     

CoPtx‐loaded Zn0.5Cd0.5S nanocomposites for enhanced visible light photocatalytic H2 production

Zn_0.5Cd_0.5S solid solution, modified with bimetallic CoPt_x nanoparticles, has been prepared using a two‐step organic solution method. The photocatalytic H₂ production rate of CoPt_x–Zn_0.5Cd_0.5S nanocomposites with different composition and percentage of CoPt_x was investigated. The results showed that the 1 wt% CoPt₃–Zn_0.5Cd_0.5S sample had the best activity which was 4.7 times higher than that of pure Zn_0.5Cd_0.5S and 1.2 times higher than that of Pt–Zn_0.5Cd_0.5S for photocatalytic H₂ production. The transient photocurrent response of the Zn_0.5Cd_0.5S showed an obvious increase in the current density after CoPt_x loading. Electrochemical impedance spectra measurements showed that the CoPt_x–Zn_0.5Cd_0.5S nanocomposites with x = 2 and 3 had lower charge transfer resistance R_t than that of Pt–Zn_0.5Cd_0.5S. The enhanced catalytic properties of the CoPt_x–Zn_0.5Cd_0.5S nanocomposites are attributed to their better accumulation ability for photoexcited electrons and higher rate for charge separation and transportation. Copyright © 2016 John Wiley & Sons, Ltd.     

A BiOCl/β‐FeOOH heterojunction for HER photocatalytic performance under visible‐light illumination

β‐iron oxide hydroxide (β‐FeOOH) had been proven to be an effective co‐catalyst during H₂ evolution reaction (HER) process. In this research, a BiOCl/β‐FeOOH heterojunction was successfully synthesized by a solid‐state doping method. Then, the structure, composition, and photo‐electrochemical properties of the prepared photocatalysts were studied. For the superior HER photocatalytic activity of ultrasmall β‐FeOOH nanoparticles (NPs) and the formation of the BiOCl/β‐FeOOH heterojunction, this heterojunction photocatalyst exhibited very superior photocatalytic performance in the HER process. Especially, when the amount of incorporated β‐FeOOH NPs was appropriate, the BFOH‐2 possessed the highest photocatalytic activity in HER process, and the HER rate was about 16.64 mmol·g^?1·h^?1 during illuminated time of 6 hours under visible light. When appropriate, ultrasmall β‐FeOOH NPs were implanted into the structure of BiOCl, the BiOCl/β‐FeOOH heterojunction interfaces would form for the existence of interfacial interactions. Therefore, this BiOCl/β‐FeOOH heterojunction exhibited superior visible‐light response, fast photo‐carrier migration, and high‐efficient separation of photo‐carriers, so that the BFOH‐2 heterojunction possessed high‐efficient hydrogen evolution reaction (HER) photocatalytic activity.     

A high‐performance CeO2@Pt‐Beta yolk‐shell catalyst used in low‐temperature ethanol steam reforming for high‐purity hydrogen production

A novel Pt‐based Beta encapsulated CeO₂ yolk‐shell catalyst was successfully synthesized via a RF layer in the synthetic process. The CeO₂@Pt‐Beta catalyst showed high catalytic activity and stability toward the LT‐ESR with respect to the reference Pt‐Beta, CeO₂‐Pt‐Beta, which benefited from the special yolk‐shell structure and the synergistic effect between the CeO₂ movable core and Pt metal. The confinement effect of the yolk‐shell architecture contributed to the high dispersion of Pt nanoparticles as well as to the accumulation of reactant molecules in the enclosed void space, which ensured the reactants reacted with CeO₂ and Pt to achieve a complete reaction.     

Enhanced surface electron transfer by fabricating a core/shell Ni@NiO cluster on TiO2 and its role on high efficient hydrogen generation under visible light irradiation

A Ni@NiO core/shell cluster was fabricated on TiO₂ surface (Ni@NiO/TiO₂) and its roles on surface electron transfer and the enhancement on hydrogen evolution under visible light irradiation were investigated. For a comparison, the Ni/TiO₂ and NiO/TiO₂ catalysts were fabricated, respectively. By photosensitization using Eosin Y as an antenna molecule, (1.6 wt%)Ni@NiO/TiO₂ exhibited the highest activity (364.1 μmol h⁻¹) in comparison with (1.6 wt%)Ni/TiO₂ and (1.6 wt%)NiO/TiO₂ and the corresponding apparent quantum efficiency reached 28.6% at 460 nm. The photoluminescence spectra and photoelectrochemical characterization results confirmed that the Ni@NiO core/shell structure could promote the photogenerated electrons transferring from TiO₂ conduction band to Ni@NiO clusters, resulting in the quicker separation of electron–hole pairs. In addition, part of NiO shell can be reduced into metallic Ni during the photoreaction and vice versa. Cyclic voltammogram characterization verified that the transformation between Ni and NiO was a dynamic balance process, which can not only provide reacting channels for electrons and protons but also ensure the photocatalytic hydrogen evolution proceeding continuously. This study discloses structure-dependent effect of non-noble metal cocatalyst on semiconductor photocatalysts in photocatalytic water reduction, and gives an insight into designing high-efficient non-noble metal/semiconductor hybrid photocatalysts.     

Composite‐modified anode by MnO2/polypyrrole in marine benthic microbial fuel cells and its electrochemical performance

Low power limits the application of microbial fuel cells (MFCs). Our research mainly focuses on the modification of the electrode and looking for new anode material for high‐power marine benthic microbial fuel cells(BMFCs). A MnO₂/PPy composite‐modified anode was fabricated by in situ chemical polymerization. Surface topography and properties were characterized by scanning electron microscopy and infrared spectroscopy, respectively, indicating that the MnO₂/PPy composite is of a ‘mosaic‐like’ microstructure. The electrochemical performance and wettability of different kinds of anode were investigated respectively. Cyclic voltammetry and linear sweep voltammetry tests show that MnO₂/PPy composite‐modified electrode has a typical capacitance feature; its capacitance is 3.1 times higher than that of unmodified electrode. Contact angle of the composite‐modified anode reduces to 46 ± 0.5°, and its kinetic activity increased for more than 1.1 times. The maximum output power density of MnO₂/PPy composite‐modified cell reached 562.7 ± 10 mW m^?2, which is 2.1‐fold of the unmodified one. Finally, the composite‐modified anode provides an alternative potential choice for high‐performance cell, and the possible influence mechanism of composite materials on the BMFCs was also analyzed. Copyright © 2016 John Wiley & Sons, Ltd.     

Chemical bath deposition synthesis of TiO2/Cu2O core/shell nanowire arrays with enhanced photoelectrochemical water splitting for H2 evolution and photostability

In this study, we have developed a facile chemical bath deposition (CBD) method to grow p-type Cu₂O nanoparticles on n-type TiO₂ nanowire arrays (TiO₂ NWAs) to fabricate TiO₂/Cu₂O core/shell heterojunction nanowire arrays (TiO₂/Cu₂O core/shell NWAs). When used as photoelectrode, the fabricated TiO₂/Cu₂O core/shell NWAs show improved photoelectrochemical (PEC) water splitting activity to pure TiO₂ NWAs. The effects of the CBD cycle times on the PEC activities have been studied. The TiO₂/Cu₂O core/shell heterojunction nanowire array photoelectrode prepared by cycling 5 times in the CBD process achieves the highest photocurrent of 2.5 mA cm^?2, which is 2.5 times higher than that of pure TiO₂ NWAs. In addition, the H₂ generation rate of this photoelectrode reaches to 32 μmol h^?1 cm^?2, 1.7 times higher than that of pure TiO₂ NWAs. Furthermore, the TiO₂/Cu₂O core/shell heterojunction nanowire array photoelectrode shows excellent photostability and achieves a stable photocurrent of over 2.3 mA cm^?2 during long light illumination time of 5 h. The enhanced photocatalytic activity of TiO₂/Cu₂O core/shell heterojunction nanowire array photoelectrode is attributed to the synergistic actions of TiO₂ and Cu₂O for improving visible light harvesting, and efficient transfer and separation of photogenerated electrons and holes.     

Development and characterization of rGO supported CdSMoS2 photoelectrochemical catalyst for splitting water by visible light

Development of a mixed phase MoS₂ (1T/2H)CdS supported on rGO photo-electrochemical catalyst for hydrogen production by splitting of water using visible light, has been reported. This catalyst showed a better efficiency compared to catalysts where either MoS₂ was incorporated with CdS or MoS₂ alone was supported on rGO. All the catalysts were photoactive under negative biasing. A detailed characterization of catalysts was performed using FTIR, XRD, DRS, HRSEM, HRTEM, SAED, XPS, and EIS etc. Higher activity of MoS₂CdS-rGO correlated with the formation of a mixed phase of MoS_2, as well as a heterojunction at the interfaces of MoS₂CdS-rGO. Formation of the heterojunction and the presence of mixed phases of MoS₂ have resulted into a better charge separation, a higher charge density and low resistance for charge transfer. These factors have attributed a higher efficiency of the catalyst. The probable mechanism of charge transfer is also discussed.     

Enhanced pseudocapacitive energy storage properties of Nb2O5/C core‐shell structures with the surface modification

Pseudocapacitive energy storage is an attractive technology as it can achieve high energy density at high rate conditions. However, its practical application has been an issue because of low electrical conductivity of nanoscale electrode materials. Surface coating is an effective way to enhance the electrochemical properties of the electrochemical energy storage system by helping electron transfer between the electrode material and current collector. In order for surface coating technologies to be applied to pseudocapacitive energy storage field, providing fast ions and electrolyte transport through the coating layer as well as high electrical conductivity is essential because pseudocapacitors aim for high rate charge/discharge capability. In this paper, the Nb₂O₅/carbon core‐shell structure is developed to meet these requirements. Simple microwave‐assisted method is applied to create nanoscale (approximately 5 nm) conductive carbon layer on the surface of bare Nb₂O₅ nanoparticles, and the high power capability of Nb₂O₅/carbon core‐shell is improved further by oxidation process providing open structure for electrolyte and ion diffusion. Thick electrode architecture containing oxidized Nb₂O₅/carbon core‐shell shows superior high rate performance as capacities of 215 C g^?1 are obtained at a 50 mV s^?1 scan rate.     

Construction of Z scheme system of ZnIn2S4/RGO/BiVO4 and its performance for hydrogen generation under visible light

A series of Z scheme systems are constructed in three ways and the photocatalytic H₂ evolution activities are evaluated under visible light irradiation. The Z scheme system can be constructed by loading ZnIn₂S₄ onto BiVO₄. The H₂ evolution is successfully realized under the visible light without providing a sacrificial agent, and the activity is greatly improved when the graphene is acted as a solid electron mediator. The best Z scheme system of 1.0La-ZnIn₂S₄/1.5RGO/1.0RuO₂/BiVO₄ (1:5) is obtained. Its photocatalytic H₂ evolution activity and the A.Q.Y. reach 4.1 μmol g^?1 h and 0.8%, respectively. Furthermore, its property is characterized by various analysis techniques, such as XRD, Raman, SEM, BET and PL, and the catalytic mechanism is also discussed.     

Ultrathin hematite films deposited layer-by-layer on a TiO2 underlayer for efficient water splitting under visible light

Ultrathin hematite (α-Fe₂O₃) film deposited on a TiO₂ underlayer as a photoanode for photoelectrochemical water splitting was described. The TiO₂ underlayer was coated on conductive fluorine-doped tin oxide (FTO) glass by spin coating. The hematite films were formed layer-by-layer by repeating the separated two-phase hydrolysis-solvothermal reaction of iron(III) acetylacetonate and aqueous ammonia. A photocurrent density of 0.683 mA cm⁻² at +1.5 V vs. RHE (reversible hydrogen electrode) was obtained under visible light (>420 nm, 100 mW cm⁻²) illumination. The TiO₂ underlayer plays an important role in the formation of hematite film, acting as an intermediary to alleviate the dead layer effect and as a support of large surface areas to coat greater amounts of Fe₂O₃. The as-prepared photoanodes are notably stable and highly efficient for photoelectrochemical water splitting under visible light. This study provides a facile synthesis process for the controlled production of highly active ultrathin hematite film and a simple route for photocurrent enhancement using several photoanodes in tandem.     

Highly efficient photocatalytic conversion of gas phase CO2 by TiO2 nanotube array sensitized with CdS/ZnS quantum dots under visible light

With the massive consumption of fossil fuels, energy crisis and effectively reducing CO₂ to curb global warming have become urgent and severe problems in the world. Photocatalytic conversion of CO₂ technology which can convert CO₂ into combustible compounds by using solar energy can solve both of the problems mentioned above. However, the photocatalytic conversion of CO₂ exhibits too low efficiency, especially under visible light. So, in order to improve the photocatalytic efficiency, the composite photocatalysts of TiO₂ nanotube array (TNTA) sensitized by CdS/ZnS quantum dots (QDs) were successfully prepared by anodization method and successive ionic layer adsorption and reaction (SILAR) method in this work. And the composite photocatalysts exhibited a high performance for photocatalytic conversion of gas-phase CO₂ to methanol under visible light. X-ray diffraction (XRD), field emission scanning electron microscope (FE-SEM), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscope (TEM), and X-ray photoelectric spectroscopy (XPS) were employed to characterize the ingredients and morphologies of the synthesized photocatalysts. And, UV–vis diffuse reflectance spectra (UV–Vis DRS) revealed that CdS/ZnS QDs enhanced the photo-absorption of composite photocatalyst in the visible light region. The main product methanol yield of CdS/ZnS-TNTA under visible light was 2.73 times that of bare TNTA when TNTA was treated by 10 SILAR cycles. Meanwhile, the product yield first increased before decreasing with the increase of the CO₂ flow rate. And the greatest product yield reached up to 255.49 nmol/(cm²-cat·h) with the increase of light intensity. The reaction mechanism was discussed in this paper. This high performance for photocatalytic reduction of CO₂ was primarily attributed to the CdS/ZnS QDs sensitization, which widens the response wavelength range of the catalyst to include visible light and partly inhibits the recombination of electron-hole pairs.     

The role of Al2Ca and Al2(Sm,Ca,La) particles in the microstructures and electrochemical discharge performance of as‐extruded Mg‐3wt.%Al‐1wt.%Zn‐based alloys for primary Mg‐air batteries

In this work, the role of Al₂Ca and Al₂(Sm,Ca,La) particles in the microstructures and electrochemical discharge performance of the as‐extruded Mg‐3wt.%Al‐1wt.%Zn‐based alloys has been reported and discussed for the anode design of Mg‐air batteries. The Al₂Ca and Al₂(Sm,Ca,La) particles strongly refine the grains of the as‐extruded AZ31 alloy from 9.1 ± 4.1 μm down to 5.1 ± 3.3 μm. The Al₂Ca and Al₂(Sm,Ca,La) particles increase the outputting cell voltage and discharge capacity of the modified AZ31 alloy. The AZ31‐Ca alloy exhibits the highest discharge capacity and anodic efficiency of 1153 mAh/g and 52.5%, respectively, at 10 mA/cm². The promoted discharge performance should be mainly attributed to the grain refinement (improving the corrosion resistance) and fine Al₂Ca phase throughout the matrix (beneficial for uniform dissolution of Mg phase). Additional Al₂(Sm,Ca,La) cubic particles further stimulate the anodic kinetics and aggravate the local dissolution of Mg phase near around, resulting in the deterioration of discharge performance.     

Surface modification of LiNi0.5Co0.2Mn0.3O2 cathode materials with Li2O‐B2O3‐LiBr for lithium‐ion batteries

LiNi_0.5Co_0.2Mn_0.3O₂ (NCM523) cathode material suffers from phase transformation and electrochemical performance degradation as its main drawbacks, which are strongly dependent on the surface state of NCM523. Herein, an effective surface modification approach was demonstrated; namely, the fast lithium‐ion conductor (Li₂O‐B₂O₃‐LiBr) was coated on NCM523. The Li₂O‐B₂O₃‐LiBr coating layer as a protecting shell can prevent NCM523 particles from corrosion by the acidic electrolyte, leading to a superior discharge capacity, rate capability, and cycling stability. At room temperature, the Li₂O‐B₂O₃‐LiBr–coated NCM523 exhibited an excellent capacity retention of 87.7% after 100 cycles at the rate of 1 C, which is remarkably better than that (29.8%) without the uncoated layer. Furthermore, the coating layer also increased the discharge capacity of NCM523 cathode material from 68.7 to 117.0 mAh g^?1 at 5 C. Those can be attributed to the reduction in the electrode polarization and improvement in the electrode conductivity, which was supported by electrochemical impedance spectroscopy and cyclic voltammetry measurements.     

Effect of anodization voltage on performance of TiO2 nanotube arrays for hydrogen generation in a two-compartment photoelectrochemical cell

Highly ordered TiO₂ nanotube arrays were prepared by anodic oxidation of Ti foil under different anodization voltages in ethylene glycol electrolyte. The morphology and photoelectrochemical performance of the TiO₂ nanotubes (NTs) samples were characterized by FESEM and electrochemical working station. Hydrogen production was measured by splitting water in the two-compartment photoelectrochemical (PEC) cell without any external applied voltage or sacrificial agent. The results indicated that anodization voltage significantly affects morphology structures, photoelectrochemical properties and hydrogen production of TiO₂ NTs. The pore diameter and layer thickness of TiO₂ samples increased linearly with the anodization voltage, which led to the enhancement of active surface area. Accordingly, the photocurrent response, photoconversion efficiency and hydrogen production of TiO₂ nanotubes were also linearly correlated with the anodization voltage.     

Promotion on electrochemical performance of Ba‐deficient Ba1 − xBi0.05Co0.8Nb0.15O3 − δ cathode for intermediate temperature solid oxide fuel cells

Reducing the operating temperature is the developing trend for solid oxide fuel cells. The key is to develop the cathode with high electrocatalytic activity for oxygen reduction reaction operated at reduced temperatures. Ba‐deficient Ba_1 ? xBi_0.05Co_0.8Nb_0.15O_3 ? δ (Ba_1 ? xBCN, 0 ≤ x ≤ 0.10) are synthesized by solid‐state reaction method and evaluated as novel cathodes for intermediate‐temperature solid oxide fuel cells. Ba_1 ? xBCN is preserved to primitive cubic perovskite phase and meets the compatibility requirement with gadolinium doped ceria oxide (GDC) electrolyte at 950°C. Though the Ba deficiency distorts the cell symmetry, it improves the charge transfer steps rapidly, ascribing to the improvement of oxygen vacancy concentration. The polarization resistance of Ba_0.95BCN is as low as 0.056 Ω cm² in air at 700°C. The peak power density of the single cell with this cathode is as high as 1.41 W cm^?2 at 750°C with wet H₂ as fuel and air as oxidant, indicating the great potential for enhanced performance of Co‐based cathodes with A‐site deficiency.