Optimal Ag concentration for H2 production via Ag:TiO2 nanocomposite thin film photoanode

TiO₂ thin films containing different concentrations of Ag nanoparticles have been synthesized by sol-gel method. According to UV–visible spectra, presence of an intense surface plasmon resonance peak at 490 nm of wavelength indicated formation of silver nanoparticles in the TiO₂ films. Based on atomic force microscopy (AFM) analysis, the surface roughness and the effective surface ratio increased by increasing the Ag mol%. Moreover, scanning electron microscopy (SEM) images showed formation of Ag nanoparticles on the surface for the samples containing high Ag concentration. X-ray diffraction (XRD) patterns revealed that the size of Ag nanocrystals increased by increasing the Ag content in the films while the nanocrystalline size of TiO₂ reduced in the presence of silver nanoparticles. Based on x-ray photoelectron spectroscopy (XPS) data, a stoichiometric chemical composition was detected for TiO₂ while, Ag presented in a combination a metal/oxide states on the surface. Studying photoresponse of the samples showed that the highest photocurrent was obtained for the sample containing 1 mol% Ag. By measuring the photovoltage versus time, it was found that addition of silver nanoparticles to the TiO₂ layer resulted in reduction of the transient time of the photogenerated carriers in the samples. Impedance spectroscopy determined a slight decrease in charge transfer resistance by addition of Ag to the films. Moreover, measuring the amount of hydrogen produced during water splitting reactions verified that the highest quantum yield of 9.6% was obtained for the sample with 1 mol% Ag.     

CIS/CdS/ZnO/ZnO:Al modified photocathode for enhanced photoelectrochemical behavior under visible irradiation: Effects of pH and concentration of electrolyte solution

In this paper, the CuInS₂ films were firstly modified with CdS and CdS/ZnO/ZnO:Al/Au layers in order to improve the photoelectrochemical (PEC) water splitting efficiency. The CuInS₂ photoelectrode was synthesized by electrodeposition method as a facial and green method, on the FTO substrate. The effects of pH and concentration of Na₂S electrolyte solution on the photocurrent density of photoelectrode samples were studied. As a p-n junction photocathode, the CIS/CdS/ZnO/ZnO:Al/Au photoelectrode indicates the enhanced PEC activity. The photocurrent density of CIS/CdS/ZnO/ZnO:Al/Au photoelectrode reaches to 1.91 mA/cm², while is about 2.5 times higher than that for CuInS₂ film at pH = 8 (−0.6 V vs Ag/AgCl). The formation of a p-n junction at the CuInS₂ photoelectrode surface not only reduces the recombination of electron-hole pairs but also increases the PEC response and water splitting performance of the as-prepared CIS/CdS/ZnO/ZnO:Al/Au photoelectrode.     

Effects of the incorporation of silver and gold nanoparticles on the photoanodic properties of rose bengal sensitized TiO2 film electrodes prepared by sol-gel method

Rose bengal-deposited TiO₂ film electrodes bearing dispersed Ag or Au nanoparticles were prepared by the sol-gel method. The dye-induced visible region photoresponse of the electrodes decreased with increasing Ag content up to a mole ratio of Ag/TiO₂ = 0.0207, while the UV photoresponse increased. On the other hand, the dye-induced visible region photoresponse decreased to a less extent by incorporation of a larger amount of Au particles of Au/TiO₂ = 0.06, along with decreased UV photoresponse. The effects of the metal particles on the dye sensitization of the electrodes were discussed in terms of band edge fluctuation induced by the surface metal particles, Schottky barriers at TiO₂/metal interfaces, and surface plasma resonance.     

Photocatalytic hydrogen production by reforming of methanol using Au/TiO2, Ag/TiO2 and Au-Ag/TiO2 catalysts

Abstract

We have investigated polyvinylalcohol stabilized Au and Ag based nanoparticles supported on titania prepared via sol immobilisation for the anaerobic, ambient temperature reforming of methanol with water for the photocatalytic production of hydrogen. The catalytic activity of the Au/TiO₂ catalysts was strongly affected by the metal loading and calcination temperature. Here, we report the preparation and use of supported Au–Ag nanoparticles, based on either the co-reduction or the consecutive reduction of the two metals. Au–Ag supported catalysts were more active than monometallic Au and Ag catalysts and the preparation methodology had a pronounced effect in terms of catalytic activity of the Au–Ag catalysts. In fact, using a consecutive reduction where Au was firstly reduced followed by reduction of Ag gave materials which exhibited the highest catalytic performance.     

Surface texturing of sputtered ZnO:Al/Ag back reflectors for flexible silicon thin-film solar cells

Al-doped zinc oxide/silver (ZnO:Al/Ag) back reflectors for silicon thin-film solar cells with an n-i-p configuration were prepared on flexible stainless steel substrates by dc magnetron sputtering. The surface morphologies of the back reflectors were modified by changing the deposition temperature of the Ag films to improve the light-scattering properties on the back reflectors, resulting in the enhancement of the light-trapping effect in the solar cells. By elevating the deposition temperature from room temperature to 500 °C, the surface roughness of the Ag films increased from 6.62 to 46.64 nm. The films at 500 °C had coarse surface features with irregular grain size distributions between 200 and 900 nm, whereas the films produced at low temperatures below 100 °C had smooth surfaces consisting of small grains between 100 and 200 nm. Even after the 100-nm thick ZnO:Al films were deposited on the modified Ag surfaces, the surface microstructure of the ZnO:Al/Ag bilayers was similar to that of the Ag films. The surface roughness of bilayers increased from 7.12 to 39.30 nm with coarsening the Ag surfaces. Haze factor (a ratio of diffuse reflectance to total reflectance) of Ag films was enhanced remarkably from 59% to 74% in a wide wavelength range from 350 to 1100 nm with increasing the surface roughness of the Ag films from 6.62 nm to 46.64 nm. Enhancement in the haze factor was due to the increase of diffuse reflectance on the Ag films, because the total reflectance did not change much with increasing surface roughness of the Ag films. This increasing roughness indicated that the light scattering from the rough surface of the back reflectors improved. The enhanced light scattering from the back reflectors influenced the performance of the solar cells mainly in terms of the short-circuit current density (J_sc). Compared to the back reflectors with smooth surface features, leading to a J_sc value of 9.94 mA/cm², the back reflectors with large surface roughness improved the J_sc value of the solar cells to 13.36 mA/cm² without detrimental changes in the fill factor (FF) and open circuit voltage (V_oc); they eventually increased the conversion efficiency of the solar cells from 5.59% to 7.60%.     

Implementation of Ag nanoparticle incorporated WO3 thin film photoanode for hydrogen production

WO₃ thin film photoanodes containing different concentrations of Ag nanoparticles were synthesized by sol–gel method. Based on UV-visible spectra, presence of a surface plasmon resonance peak at 470 nm of wavelength indicated formation of silver nanoparticles in the WO₃ films. According to atomic force microscopy (AFM) analysis, the highest value for surface roughness and the effective surface ratio was observed for the sample containing 2 mol% of Ag. X-ray diffraction (XRD) patterns revealed that WO₃ nanocrystalline structure was formed in the monoclinic phase with the average size of about 18.2 nm while Ag nanocrystals were determined in cubic phase. X-ray photoelectron spectroscopy (XPS) showed that Ag exists in a combination of metal/oxide states on the surface. Photoresponse investigation of the synthesized films indicated that the highest photocurrent was obtained for the sample containing 2 mol% Ag with the maximum incident photon to current efficiency (IPCE) of about 20% at 360 nm wavelength. Moreover, measuring the amount of hydrogen produced during water splitting reactions verified that the highest hydrogen production rate (∼3 μmol/h) was obtained for the sample with 2 mol% Ag.     

Structure and optical properties of M/ZnO (M=Au, Cu, Pt) nanocomposites

Metal (Au, Cu, Pt)/zinc oxide nanocomposite films were prepared with different metal contents by radio frequency co-sputtering technique. The films were annealed at different temperatures in an argon atmosphere for 2 h. Formation of metal nanoparticles was studied by transmission electron microscopy (TEM) and X-ray diffraction (XRD). UV-Vis optical absorption spectroscopy was used for optical characterization of the samples. With the increase of annealing temperature, the size of the metal particles in the ZnO matrix varied. Surface plasmon resonance bands were observed in the Au/ZnO and Cu/ZnO composite films due to the formation of nanometer-size Au and Cu particles in the matrix. However, a similar behavior was not seen with Pt/ZnO composites. Upon incorporation of Pt nanoparticles in the ZnO matrix, the optical band gap of the matrix was drastically reduced.     

Effect of Au,Ag and Cu thin films' thickness on the electrical parameters of metal-porous silicon direct hydrogen fuel cell

The effect of the thickness of the gold, silver and cupper films on the electrical properties such as open circuit voltage (V_oc) and short circuit current (I_sc), in the direct hydrogen fuel cell, which uses water as a source of hydrogen, is studied by fabricating Metal/Porous Silicon/n-Silicon/Indium structures. The Porous Silicon (PS) layer on n-type (111) oriented silicon wafers were prepared by anodization. The thin films of Au or Ag or Cu with different thicknesses between 120 and 600 nm were deposited onto the PS surface by the electron-beam technique. The obtained results indicated that V_oc and I_sc, strongly depend on the Au, Ag and Cu layer thicknesses. The Au/PS/n-Si structure generated highest V_oc and I_sc values for all thicknesses of Au film. The best values of V_oc and I_sc were obtained at 325 nm as 0.89 V and 0.021 mA for Au, at 350 nm as 0.75 V and 0.017 mA for Ag, at 350 nm as 0.50 V and 0.010 mA, respectively.     

Enhanced photocatalytic hydrogen production from aqueous methanol solution using ZnO with simultaneous photodeposition of Cu

The enhanced photocatalytic hydrogen production from aqueous methanol solution using ZnO was investigated with aid of simultaneous metal deposition. The simultaneous deposition for such metals as Ag, Au, Cu, Ni, Pd, Pt, and Rh was evaluated for the H₂ production from aqueous methanol solution. As a result, the addition of Cu ion was effective improvement in photocatalytic hydrogen evolution. The photocatalytic hydrogen production using ZnO photocatalyst with aid of simultaneous deposition of Cu was approximately 130 times better than those obtained with bare ZnO. The Cu-deposited ZnO had the response to the visible light for the hydrogen formation. After the photocatalytic hydrogen production, the in-situ Cu-photodeposited ZnO sample was characterized by X-ray diffraction (XRD), UV–visible diffuse reflectance spectrometry (UV-DRS), and photoluminescence (PL) spectroscopy.     

In-situ and ex-situ comparison of the electrochemical oxidation of SO2 on carbon supported Pt and Au catalysts

Electrochemical characterizations are performed using thin films and commercial carbon supported platinum and gold catalysts for sulfur dioxide oxidation, the primary electrochemical oxidation reaction in the Hybrid-sulfur (HyS) thermochemical process. Electrochemical evaluation of metal thin films qualitatively confirms the higher activity of Au over Pt, AuPt, Pd, and Ir for the electrochemical oxidation of SO₂. Ex-situ testing, using rotating disk electrode (RDE), shows an earlier onset potential for Au/C at low sulfuric acid concentrations (C ≤ 3.5 M) and a higher turnover frequency than Pt/C at sulfuric acid concentrations ranging from 3.5 M to 9 M. In-situ electrolysis experiments using low catalyst loadings (0.1 mg_Au cm⁻², a factor of ≥5 lower than typical loadings) confirm that Au nanoparticles exhibit higher current densities and greater stability than Pt nanoparticles. This is consistent with the thin film screening studies, which showed higher activity with increasing gold content in AuPt thin films. This work reveals an alternative material to state-of-the-art Pt to lower the energy needs and aid the HyS cycle in reaching the target of $2/kg H₂ set forth by the Department of Energy to achieve economic feasibility of large-scale hydrogen generation.     

Catalytic activities of Ag/C decorated with small amounts of Au and Pt for glycerol oxidation

The two-step decoration of the Ag nanoparticles supported on carbon black (Ag/C) with Au and Pt, the electrooxidation of glycerol on the Pt/Au/Ag/C catalysts in alkaline solution, and the effect of the amounts of Au and Pt on the catalytic activity of Pt/Au/Ag/C are investigated. The decoration of Ag/C is performed by electrochemically depositing a small amount of Au and then Pt on Ag/C, and the Pt_x/Au_y/Ag₁₀₀/C catalysts with different x:y:100 ratios (0.15 ≤ x ≤ 1.9 and 0.2 ≤ y ≤ 1.5) are obtained. Physical and electrochemical characterizations reveal that small parts of the Ag surfaces are covered by the deposited Au and Pt. Pt_x/Au_y/Ag₁₀₀/C mainly shows Pt-relevant behaviors in glycerol oxidation, and Pt_1.3/Au_y/Ag₁₀₀/C exhibits high catalytic activities. The results reveal that the surface decoration is a useful method of fabricating efficient ternary catalysts at low cost.     

Enhancing the photocatalytic hydrogen production of the ZnO–TiO2 heterojunction by supporting nanoscale Au islands

In this work, Au was loaded on the ZnO–TiO₂ heterojunction by the deposition-precipitation with urea method to boost its photocatalytic hydrogen production. The synthesized materials were characterized by TEM, ICP-OES, XRD, N₂ adsorption-desorption, UV–vis spectrophotometry, XPS, and (photo)electrochemical measurements. The TEM images confirmed the close contact between ZnO and TiO₂ nanoparticles and showed that although Au nanoparticles agglomerated in the form of islands; they were widely dispersed on the surface of the photocatalysts. Besides, the XPS characterization revealed the enhanced contribution by the metallic Au species as their amount was increased in the composite. The heterojunctions with different Au contents produced higher yield in the photocatalytic production of hydrogen, observing a maximum with the 2-wt.%- Au content (9.13 mmol g⁻¹), being this value 6 times higher than the results obtained with the ZnO–TiO₂ heterojunction. This improvement is associated with the synergistic interaction between the ZnO–TiO₂ heterojunction and Au islands that promoted the separation and transfer of charge carriers. Besides, the (photo)electrochemical characterization showed that the islands acted as “electronic reservoirs”, prolonging the lifetime of the photogenerated electron-hole pairs and creating surface or energy states at the Au/ZnO–TiO₂ heterojunction interface. These states helped improve the charge transfer processes by diminishing the recombination and increasing the photocatalytic hydrogen production.     

Three-dimensional ZnO@TiO2 core-shell nanostructures decorated with plasmonic Au nanoparticles for promoting photoelectrochemical water splitting

A novel three-dimensional (3D) core-shell nanostructure decorated with plasmonic Au nanoparticles (NPs) was prepared for photoelectrochemical water splitting. In the new nanostructure, ZnO nanorods (NRs) are perpendicular to ZnO nanosheets (NSs), and the ZnO NSs-NRs are coated with a thin TiO₂ shell formed by liquid phase deposition. The plasmonic Au NPs were formed in situ on the surface of ZnO NSs-NRs@TiO₂ by thermal reduction. A thin TiO₂ shell and uniformly distributed Au NPs were successfully obtained. The photoconversion efficiency and photocurrent density of the 3D ZnO NSs-NRs@TiO₂-Au nanostructure respectively reached 0.48% and 1.73 mA cm⁻² at 1.23 V vs. reversible hydrogen electrode, 4.80 and 4.33 times higher than those of ZnO NSs, respectively. The thin TiO₂ shell effectively promoted charge separation, while the surface plasmon resonance effects of the Au NPs improved the photocurrent density. The findings suggest that the 3D ZnO NSs-NRs@TiO₂-Au nanostructure is a promising photoanode for photoelectrochemical water splitting.     

Biomass-derived hierarchical porous CdS/M/TiO2 (M = Au,Ag, pt,pd) ternary heterojunctions for photocatalytic hydrogen evolution

We demonstrate a general method for the synthesis of biomass-derived hierarchical porous CdS/M/TiO₂ (M = Au, Ag, Pt, Pd) ternary heterojunctions for efficient photocatalytic hydrogen evolution. A typical biomass—wood are used as the raw sources while five species of wood (Fir, Ash, White Pine, Lauan and Shiraki) are chosen as templates for the synthesis of hierarchical porous TiO₂. The as-obtained products inherited the hierarchical porous features with pores ranging from micrometers to nanometers, with improved photocatalytic hydrogen evolution activity than non-templated counterparts. Noble metals M (M = Pt, Au, Ag, Pd) and CdS are loaded via a two-step photodeposition method to form core (metal)/shell (CdS) structures. The photocatalytic modules—CdS(shell)/metal (core)/TiO₂ heterostructures, have demonstrated to increase visible light harvesting significantly and to increase the photocatalytic hydrogen evolution activity. The H₂ evolution rates of CdS/Pd/TiO₂ ternary heterostructures are about 6.7 times of CdS/TiO₂ binary heterojunctions and 4 times higher than Pd/CdS/TiO₂ due to the vertical electron transfer process. The design of such system is beneficial for enhanced activity from morphology control and composition adjustment, which would provide some new pathways for the design of promising photocatalytic systems for enhanced performance.     

Sensitization of nano-porous ZnO photo-anode by a conjugated conducting polymer

Hybrid ZnO films are prepared via one-step electrochemical process. Extraction of organic component from hybrid films results tiny wires like ZnO columns perpendicular to the substrate. Visible light sensitive-conjugated polymer poly(2-methoxy-5-[2 ethylhexyloxy]-1-4-phenylenevinylene, MEH–PPV) was embedded in highly porous ZnO ceramic by a solvent vaporization technique. An attempt was made to fabricate polymer sensitized photovoltaic cell by coupling polymer embedded ZnO electrodes with an electrolyte. Maximum photovoltage of 490 mV is observed for the cell with the configuration of ZnO|MEH–PPV|I^?/I₃^? cell.     

Preparation of ZnO thin films using MOCVD technique with D2O/H2O gas mixture for use as TCO in silicon-based thin film solar cells

Zinc oxide (ZnO) thin films have been successfully grown by metal organic chemical vapor deposition (MOCVD) technique using deuterium water (D₂O) and water (H₂O) mixtures as oxidants for diethylzinc (DEZ). B₂H₆ was also employed as a dopant gas. It was found that the crystal orientation of ZnO films strongly depends on D₂O/H₂O ratio. As a result, the surface morphology of ZnO changed from textured surface morphology to smooth surface morphology with increase in the ratio of D₂O/H₂O. Moreover, it was also observed that the carrier concentration of ZnO films did not change with the ratio of D₂O/H₂O, while the mobility of these films was strongly dependent on the D₂O/H₂O ratio. Without D₂O addition, the resistivity of films had its lowest value and the minimum sheet resistance was 10 Ω/square. All films showed transmittance higher than 80% in the visible region. Moreover, the haze values of these films could be controlled by the ratio of D₂O/H₂O. These results indicate that the crystal orientation and surface morphology of the low resistivity ZnO films can be modified by using a mixture of D₂O and H₂O without changing the deposition temperature. Thus, the obtained ZnO films are promising for use as a front TCO layer in Si-based thin film solar cells.     

Fast in-situ photodeposition of Ag and Cu nanoparticles onto AgTaO3 perovskite for an enhanced photocatalytic hydrogen generation

The M (M = Ag, Cu) nanoparticles were deposited by a fast in-situ photoreduction method onto the AgTaO₃ photocatalyst surface using 1, 2, and 5 wt % ratios, in order to investigate their photocatalytic properties for hydrogen production. The obtained results indicated a nanoparticles growth <20 nm in diameter during 10 min of photoreduction process for both nanoparticles. The M (M = Ag, Cu) NPs/AgTaO₃ exhibited superior photocatalytic activity than bare AgTaO₃, with an efficiency increment of around 11 and 30 times at 2 wt % ratio of Ag and Cu nanoparticles, respectively. The excellent photocatalytic activity could be related to the surface plasmon resonance effect of nanoparticles, preventing the electron-hole recombination. Additionally, the optical and photoelectrochemical characterization revealed the presence and the effect of oxidized species of the nanoparticles, with a direct impact on the transport of photogenerated charge carriers for the improvement of the photocatalytic activity.     

Enhanced catalytic performance of Au/CuO–ZnO catalysts containing low CuO content for preferential oxidation of carbon monoxide in hydrogen-rich streams for PEMFC

In this study, effects of Au and CuO loadings in Au/CuO–ZnO nanocatalysts for preferential oxidation of carbon monoxide in H₂-rich streams (PROX) are investigated. CuO–ZnO supports were synthesized by a co-precipitation method. Au was also incorporated into the catalysts by a deposition-precipitation procedure. The catalysts were characterized by XRD, BET surface area, FESEM, HRTEM, H₂-TPR, FTIR, and CO-TPD. 2–10 nm Au nanoparticles are dispersed on CuO–ZnO support and significantly enhance the reducibility of CuO. The Au/CuO–ZnO catalysts containing low amount of CuO were found to be more active for PROX compared to the Au/ZnO catalyst. Moreover, as more CuO is added to Au/ZnO, the CO₂ selectivity increases in the whole PROX temperature range. The catalyst containing 2 wt% Au and 1 wt% CuO on ZnO exhibited the highest activity and selectivity in the operating temperature range of PEM fuel cells. The activity of this catalyst also remained almost intact during 900 min of PROX time on stream at 80 °C.     

Metal oxide nanoparticles synthesized by pulsed laser ablation for proton exchange membrane fuel cells

We report on the development of a modified gas diffusion layer for fuel cells consisting of a simple or teflonized carbon cloth pulsed laser deposited with metal oxide nanostructures designed to operate both as co-catalyst, and oxidic support for other electrochemically active catalysts. We selected TiO₂, ZnO and Al₂O₃ doped (2 wt.%) ZnO which were uniformly distributed over the surface of gas diffusion layers in order to improve the catalytic activity, stability and lifetime, and reduce the production costs of proton exchange membrane fuel cells. We evidenced by scanning electron microscopy and energy dispersive spectroscopy that our depositions consisted of TiO₂ nanoparticles while in the case of ZnO and Al₂O₃ doped (2 wt.%) ZnO transparent quasi-continuous films were synthesized.     

Hydrogen sensing using gold nanoclusters supported on tungsten trioxide thin films

Controlled amounts of chemically synthesised gold (Au) nanoclusters were deposited onto tungsten trioxide (WO₃) nanostructured thin films as sensors for hydrogen. The Au/WO₃ thin films were characterised by XPS, XRD, SEM and TEM. Performance of Au/WO₃ films was tested at operating temperatures varying from room temperature to 450 °C. It was demonstrated that Au metal loading plays an important role in defining enhancement of the sensor response towards hydrogen. “Less is more” principle applies to the reported here sensors as materials made using lower concentration of Au nanoclusters demonstrated significantly better response. HRTEM images of the Au/WO₃ thin films provide evidence that the more active sensors are enriched with smaller Au nanoparticles (≤5 nm). Fast response towards H₂ within a wide range of industrially relevant concentrations, excellent baseline stability and signal reproducibility at optimized operating temperature demonstrate feasibility of this novel approach toward fabrication of sensors.