Atomic layer deposition of rhodium and palladium thin film using low-concentration ozone

Rhodium (Rh) and palladium (Pd) thin films have been fabricated using an atomic layer deposition (ALD) process using Rh(acac)₃ and Pd(hfac)₂ as the respective precursors and using short-pulse low-concentration ozone as the co-reactant. This method of fabrication does away with the need for combustible reactants such as hydrogen or oxygen, either as a precursor or as an annealing agent. All previous studies using only ozone could not yield metallic films, and required post treatment using hydrogen or oxygen. In this work, it was discovered that the concentration level of ozone used in the ALD process was critical in determining whether the pure metal film was formed, and whether the metal film was oxidized. By controlling the ozone concentration under a critical limit, the fabrication of these noble metal films was successful. Rhodium thin films were deposited between 200 and 220 °C, whereas palladium thin films were deposited between 180 and 220 °C. A precisely controlled low ozone concentration of 1.22 g m⁻³ was applied to prevent the oxidation of the noble metallic film, and to ensure fast growth rates of 0.42 Å per cycle for Rh, and 0.22 Å per cycle for Pd. When low-concentration ozone was applied to react with ligand, no excess ozone was available to oxidize the metal products. The surfaces of deposited films obtained the RMS roughness values of 0.30 nm for Rh and 0.13 nm for Pd films. The resistivities of 18 nm Rh and 22 nm Pd thin films were 17 μΩ cm and 63 μΩ cm.

Rh and Pd metallic thin films were fabricated by atomic layer deposition using Rh(acac)₃ and Pd(hfac)₂ precursors, and only low-concentration ozone as co-reactant.     

Effects of morphology and pore size of mesoporous silicas on the efficiency of an immobilized enzyme

An investigation is performed into the efficiency of the Streptomyces griseus HUT 6037 enzyme immobilized in three different mesoporous silicas, namely mesoporous silica film, mesocellular foam, and rod-like SBA-15. It is shown that for all three supports, the pH value changes the surface charge and charge density and hence determines the maximum loading capacity of the enzyme. The products of the enzyme hydrolytic reaction are analyzed by ¹H-NMR. The results show that among the three silica supports, the mesoporous silica film (with a channel length in the range of 60–100 nm) maximizes the accessibility of the immobilized enzyme. The loading capacity of the enzyme is up to 95% at pH 7 and the activity of the immobilized enzyme is maintained for more than 15 days when using a silica film support. The order of the activity of the enzyme immobilized in different mesoporous silica supports is: mesoporous silica film > mesocellular foam > rod-like SBA-15. Furthermore, the immobilized enzyme can be easily separated from the reaction solution via simple filtration or centrifugation methods and re-used for hydrolytic reaction as required.

Mesoporous silica films were used as supports with high loading capacity and enzyme activity.     

Gravure printing for mesoporous film preparation

This study presents gravure printing as a new strategy for rapid printing of ceramic mesoporous films and highlights its advantages over conventional mesoporous film preparation using evaporation induced self-assembly together with dip-coating. By varying the printing process parameters, the mesoporous coating thicknesses can be adjusted between 20 and 200 nm while maintaining a very high film homogeneity allowing the printing of ultrathin mesoporous films. Step gradients in film composition are accessible by consecutively printing two different “inks”. Thereby, gravure printing is a much faster process than mesoporous single- and multilayer preparation using conventional dip-coating because lower amounts of solution are transferred and dissolution of previously deposited layers is avoided. The effect of printing process parameters on resulting film characteristics as well as the resulting mesoporous film''s ionic accessibility is systematically investigated.

This study presents gravure printing as a new strategy for rapid printing of ceramic mesoporous thin films and highlights its advantages over conventional mesoporous film preparation using evaporation induced self-assembly together with dip-coating.      

Study on the selective hydrogenation of isophorone

3,3,5-Trimethylcyclohexanone (TMCH) is an important pharmaceutical intermediate and organic solvent, which has important industrial significance. The selective hydrogenation of isophorone was studied over noble metal (Pd/C, Pt/C, Ir/C, Ru/C, Pd/SiO₂, Pt/SiO₂, Ir/SiO₂, Ru/SiO₂), and non-noble metal (RANEY® Ni, RANEY® Co, RANEY® Cu, RANEY® Fe, Ni/SiO₂, Co/SiO₂, Cu/SiO₂, Fe/SiO₂) catalysts and using solvent-free and solvent based synthesis. The results show that the solvent has an important effect on the selectivity of TMCH. The selective hydrogenation of isophorone to TMCH can be influenced by the tetrahydrofuran solvent. The conversion of isophorone is 100%, and the yield of 3,3,5-trimethylcyclohexanone is 98.1% under RANEY® Ni and THF. The method was applied to the selective hydrogenation of isopropylidene acetone, benzylidene acetone and 6-methyl-5-ene-2-heptanone. The structures of the hydrogenation product target (4-methylpentan-2-one, 4-benzylbutan-2-one and 6-methyl-heptane-2-one) were characterized using ¹H-NMR and ¹³C-NMR. The yields of 4-methylpentan-2-one, 4-benzylbutan-2-one and 6-methyl-heptane-2-one were 97.2%, 98.5% and 98.2%, respectively. The production cost can be reduced by using RANEY® metal instead of noble metal palladium. This method has good application prospects.

The selective hydrogenation of isophorone to TMCH can be influenced by the tetrahydrofuran solvent. The conversion of isophorone is 100%, and the yield of 3,3,5-trimethylcyclohexanone is 98.1% under RANEY® Ni and THF.     

Mesoporous TiO2 anatase films for enhanced photocatalytic activity under UV and visible light

Mesoporous TiO₂ films with enhanced photocatalytic activity in both UV and visible wavelength ranges were developed through a non-conventional atomic layer deposition (ALD) process at room temperature. Deposition at such a low temperature promotes the accumulation of by-products in the amorphous TiO₂ films, caused by the incomplete hydrolysis of the TiCl₄ precursor. The additional thermal annealing induces the fast recrystallisation of amorphous films, as well as an in situ acidic treatment of TiO₂. The interplay between the deposition parameters, such as purge time, the amount of structural defects introduced and the enhancement of the photocatalytic properties from different mesoporous films clearly shows that our easily upscalable non-conventional ALD process is of great industrial interest for environmental remediation and other photocatalytic applications, such as hydrogen production.

Mesoporous TiO₂ films with enhanced photocatalytic activity in both UV and visible wavelength ranges were developed through a non-conventional atomic layer deposition (ALD) process at room temperature.     

Configurable 2D nano-flows in mesoporous films using paper patches

Designing and controlling spontaneous imbibition is becoming a key requirement for advanced devices, presenting a substantial scientific and engineering challenge. Here we describe an approach that allows directional imbibition into designed geometries. A set of custom domains based on paper microfluidics mold nano-imbibition in user-defined shapes such as curvatures, corners, and vertices into mesoporous thin films; enabling localized chemical reactions with programmable designs. The method also achieves nano-size filtration, allows the generation and delivery of reagent gradients in a nanofluidic fashion, and it can be used as a reactor for the synthesis of patterned metallic nanoparticle arrays. By using this easy-to-build hybrid platform, users can create functional nanofluidic domains in custom geometries and perform spatially shaped chemistry. The ability to integrate mesoporous nanofluidic generation and paper-based microfluidics has made the hybrid system an exciting candidate for versatile nanoflow applications.

Mesoporous film-based nanofluidics has been converted into a versatile technique by using cut paper.     

A highly efficient nano-sized Cu2O/SiO2 egg-shell catalyst for C–C coupling reactions

Mesoporous SiO₂-supported Cu₂O nanoparticles as an egg-shell type catalyst were prepared by impregnation method. The obtained Cu₂O/SiO₂ egg-shell nanocatalyst had a large surface area and narrow pore size distribution. In addition, most of the Cu₂O nanoparticles, with sizes around 2.0 nm, were highly dispersed in the mesoporous silica. Accordingly, fast reactant diffusion to the active sites would occur, especially when the active metal sites are selectively located on the outer part of the support, i.e., the outer region of the egg shell. In solvent-free Sonogashira reactions for the synthesis of ynones from acyl chlorides and terminal alkynes, this catalyst exhibited a very high catalytic activity. The excellent catalytic performance can be attributed to the synergistic advantages of mesoporous structure and monodispersed Cu₂O nanoparticles.

Mesoporous SiO₂-supported Cu₂O nanoparticles as an egg-shell type catalyst were prepared by impregnation method.     

Synthesis of a mesoporous titania thin film with a pseudo-single-crystal framework by liquid-phase epitaxial growth,and enhancement of photocatalytic activity

A mesoporous titania thin film with a pseudo-single-crystal framework was synthesized on a lanthanum aluminate single-crystal substrate by a surfactant-assisted sol–gel method and liquid-phase epitaxial growth. The crystal lattices were well aligned within the titania framework. The highly energetic {001} facet was exposed on the top surface, which significantly enhanced the photocatalytic activity.

An anatase-phase mesoporous titania thin film with a pseudo-single-crystal framework was facilely synthesized by an inexpensive chemical process.     

Theoretical analyses on water cluster structures in polymer electrolyte membrane by using dissipative particle dynamics simulations with fragment molecular orbital based effective parameters

The mesoscopic structures of polymer electrolyte membrane (PEM) affect the performances of fuel cells. Nafion® with the Teflon® backbone has been the most widely used of all PEMs, but sulfonated poly-ether ether-ketone (SPEEK) having an aromatic backbone has drawn interest as an alternative to Nafion. In the present study, a series of dissipative particle dynamics (DPD) simulations were performed to compare Nafion and SPEEK. These PEM polymers were modeled by connected particles corresponding to the hydrophobic backbone and the hydrophilic moiety of sulfonic acid group. The water particle interacting with Nafion particles was prepared as well. The crucial interaction parameters among DPD particles were evaluated by a series of calculations based on the fragment molecular orbital (FMO) method in a non-empirical way (Okuwaki et al., J. Phys. Chem. B, 2018, 122, 338–347). Through the DPD simulations, the water and hydrophilic particles aggregated, forming cluster networks surrounded by the hydrophobic phase. The structural features of formed water clusters were investigated in detail. Furthermore, the differences in percolation behaviors between Nafion and SPEEK revealed much better connectivity among water clusters by Nafion. The present FMO-DPD simulation results were in good agreement with available experimental data.

The mesoscopic structures of polymer electrolyte membrane (PEM) affect the performances of fuel cells.     

Well-dispersed Pd nanoparticles on porous ZnO nanoplates via surface ion exchange for chlorobenzene-selective sensor

The extensive use of chlorobenzene in chemical, pharmaceutical, and agrochemical industries poses a severe health hazard to human beings, because it is highly toxic. The detection of chlorobenzene by metal oxide gas sensors is difficult, owing to its chemically inert molecular structure. In this study, well-dispersed Pd nanoparticles were deposited on porous ZnO nanoplates via surface ion exchange, followed by H₂ reduction. The preparation process effectively prevented the aggregation and uncontrollable growth of Pd particles. A gas-sensing test was conducted, and the modification of size-controlled Pd nanoparticles was found to effectively enhance the sensing properties of porous ZnO nanoplates to chlorobenzene over 300 °C (higher sensitivity at a low operating temperature). At 440 °C, 5% Pd@ZnO sensor showed a drastic increase in response by nearly 4.5-fold, as well as excellent sensing selectivity to chlorobenzene. Its repeatability and stability were acceptable. As known, Pd nanocatalysts contribute to the oxidation of chlorinated aromatic compounds. Pd@ZnO sensors generated more catalytic sites and oxygen species (confirmed by XPS), thus enhancing chlorobenzene oxidation and improving the sensitivity of ZnO-based gas sensors.

Well-dispersed and size-controlled Pd nanocatalysts were deposited on porous ZnO nanoplates via surface ion exchange for enhanced and selective chlorobenzene-sensor.     

Mechanical behavior of a hydrated perfluorosulfonic acid membrane at meso and nano scales

Perfluorosulfonic acid (PFSA) is widely used as the membrane material for proton-exchange membrane fuel cells, and its mechanical properties directly affect the stability and the life of the internal structure of the proton exchange membrane. In the present research, mechanical behaviors of hydrated membranes are investigated through macro-mechanical experiments and nano-simulation. The commercial products of Nafion® 117 and Nafion® 212 are used as tensile testing samples, and the latter manifests a larger swelling ratio, smaller linear-elastic region, and higher Young''s modulus at the same humidity. It is found that in comparison to Nafion 117, humidity (especially at less than 9 wt%) yields profound effects on true stress–true strain curves of Nafion 212. Further, two types of PFSA ionomers, representing the nanoscale parts of Nafion and Aquivion membranes, respectively, are studied on the uniaxial tensile deformation through molecular dynamics simulation, and the effects of side chain, water content, backbone length, and strain rate are examined. It is noticed that long side chains decrease the winding degree of polymer chains for the PFSA ionomers with the same backbone, and pinhole failure causes the declining trend of stress–strain curves. For meso- and nano-scale PFSA polymers, the difference between the volume of uptake water and swelling volume can be used to roughly judge the aggregation degree of polymer chains and explain the elastic–plastic deformation mechanism. The results of this work will serve as a baseline for understanding the swelling and mechanical behavior of PFSA membranes.

Perfluorosulfonic acid (PFSA) is widely used as the membrane material for proton-exchange membrane fuel cells, and its mechanical properties directly affect the stability and the life of the internal structure of the proton exchange membrane.     

Synthesis of Pd-loaded mesoporous SnO2 hollow spheres for highly sensitive and stable methane gas sensors

High performance methane gas sensors have become more and more essential in different fields such as coal mining, kitchens and industrial production, which necessitates the design and synthesis of highly sensitive materials. Herein, mesoporous SnO₂ hollow spheres with high surface area (>90 m² g⁻¹) are prepared by a progressive inward crystallization routine, showing a high response of 1.31 to 250 ppm CH₄ at a working temperature of 400 °C. Furthermore, loading noble metal Pd onto the surface of SnO₂ hollow spheres by an adsorption–calcination process improves the response to 4.88 (250 ppm CH₄) at the optimal dosage of 1 wt% Pd. Meanwhile, the working temperature decreases to 300 °C, showing the prominent spillover effect of catalytic Pd and PdO–SnO₂ heterostructure sensitization as evidenced by the binding energy shift in the X-ray photoelectron spectroscopy (XPS) analysis. The response/recovery time is as short as 3/7 s and the sensitivity is stable for a test period as long as 15 weeks. All these performances show the promise of the highly porous Pd-loaded SnO₂ hollow spheres for high performance methane sensors.

This work reports a simple, rapid, effective and reliable CH₄ sensor based on Pd-loaded SnO₂ hollow spheres with high surface area and porosity, which is of great importance to gas sensing performance.     

Water-assisted synthesis of mesoporous calcium carbonate with a controlled specific surface area and its potential to ferulic acid release

A carbonation process to control the specific surface area of mesoporous calcium carbonate and the dissolution profile of ferulic acid on mesoporous carbonate particles are presented. The effects of water content on the physicochemical properties, specific surface area, pore size, crystallinity, and morphology are evaluated. Mesoporous calcium carbonate particles are synthesised with well-controlled specific surface areas of 38.8 to 234 m² g⁻¹. Each of the submicron-size secondary particles consists of a primary particle of nano-size. During secondary particle formation, primary particle growth is curbed in the case with less water content. By contrast, growth is promoted via dissolution and recrystallisation in the presence of water. The release rates of ferulic acid are gradually enhanced with increasing specific surface area of the mesoporous calcium carbonate, that reflects crystallinity of ferulic acid.

A carbonation process to control the specific surface area of mesoporous calcium carbonate and the dissolution profile of ferulic acid on mesoporous carbonate particles are presented.     

Obtention of biodiesel through an enzymatic two-step process. Study of its performance and characteristic emissions

We describe the enzymatic synthesis of biodiesel from waste cooking oil (WCO) in a two-step production process: hydrolysis of WCO, followed by acid-catalyzed esterification of free fatty acids (FFAs). Among the three commercial enzymes evaluated, the inexpensive lipase Lipex® 100L supported on Lewatit® VP OC 1600 produced the best overall biodiesel yield (96.3%). Finally, we assessed the combustion efficiency of the obtained biodiesel and its blends. All blends tested presented lower emissions of CO and HC compared to diesel. The NOx emissions were higher due to biodiesel''s high volatility and viscosity. The cost of biodiesel production was calculated using the process described.

The inexpensive lipase Lipex® 100L produced biodiesel from waste cooking oil in a two-step process, with an overall yield of 96.3%.     

Roll-to-roll processed,highly conductive,and flexible aluminum (Al) electrodes based on Al precursor inks

In this study, a roll-to-roll (R2R) process for the large-scale fabrication of aluminum thin films on flexible polyimide (PI) films is proposed. The R2R machine for Al-film coating assembled in the current work uses a previously reported Al etherate-based precursor ink as the source. After the PI substrate is exposed to a diluted catalyst, the Al precursor ink is coated directly on to the substrate by a slit-die coating method. To optimize the injection of the Al precursor ink, a low-flow limit was established. At a film speed of 5 cm s⁻¹, the width of the fabricated Al film was 130 mm. Such Al-coated films exhibit many advantageous features, including 5.87 × 10⁶ S m⁻¹ of high electrical conductivity at 60.9 nm film thickness and high durability with good adhesion. There was only a minor change in the resistance of the film when it was heated at 100 °C in an oven for 10 days or when it was exposed to H₂O or ethyl alcohol. Flexibility and tape testing was also conducted and the film showed robustness in both cases. Touch panels (7 cm × 9 cm) were fabricated using the fabricated Al-coated film as one side of the panel; the panel showed enough sensitivity to write recognizable letters on the computer. This indicates that the fabricated Al films can be applied in actual electronic devices without further complicated processing.

R2R machine is designed for the Al thin film coating to the flexible substrate, and the substrate can be applied to the flexible electronics.     

Stability of MAPbI3 perovskite grown on planar and mesoporous electron-selective contact by inverse temperature crystallization

Single crystalline perovskite solar cells (PSC) are promising for their inherent stability due to the absence of grain boundaries. While the development of single crystals of perovskite with enhanced optoelectronic properties is known, studies on the growth, device performance and understanding of the intrinsic stability of single crystalline perovskite thin film solar cell devices fabricated on electron selective contacts are scarcely explored. In this work, we examine the impact of mesoporous TiO₂ (m-TiO₂) and planar TiO₂ (p-TiO₂) on the growth of single crystalline-methyl ammonium lead iodide (SC-MAPbI₃) film, PSC device performance and film stability under harsh weather conditions (T ∼ 85 °C and RH ∼ 85%). Self-grown SC-MAPbI₃ films are developed on m-TiO₂ and p-TiO₂ by inverse temperature crystallization under ambient conditions without the need for sophisticated glove-box processing. The best device with m-TiO₂ as an electron transport layer showed a promising power conversion efficiency of 3.2% on an active area of 0.3 cm² in hole transport material free configuration, whereas, only 0.7% was achieved for the films developed on p-TiO₂. Complete conversion of precursor to perovskite phase and better surface coverage of the film leading to enhanced absorption and reduced defects of single crystalline perovskite on m-TiO₂ compared to its p-TiO₂ leads to this large difference in efficiency. Mesoporous device retained more than 70% of its initial performance when stored at 30 °C under dark for more than 5000 h at 50% RH; while the planar device degraded after 1500 h. Thermal and moisture endurance of SC-MAPbI₃ films are investigated by subjecting them to temperatures ranging from 35 °C to 85 °C at a constant relative humidity (RH) of 85%. X-ray diffraction studies show that the SC-MAPbI₃ films are stable even at 85 °C and 85% RH, with only slight detection (30–35%) of PbI₂ at these conditions. This study highlights the superior stability of SC-MAPbI₃ films which paves way for further studies on improving the stability and performance of the ambient processed PSCs.

MAPbI₃ film grown on mesoporous TiO₂ showed better crystallinity, performance and stability compared to its planar counterpart.     

Difference in structural and chemical properties of sol–gel spin coated Al doped TiO2, Y doped TiO2 and Gd doped TiO2 based on trivalent dopants

In this research, pure titanium dioxide (TiO₂) and doped TiO₂ thin film layers were prepared using the spin coating method of titanium(iv) butoxide on a glass substrate from the sol–gel method and annealed at 500 °C. The effects on the structural and chemical properties of these thin films were then investigated. The metal doped TiO₂ thin film which exists as trivalent electrons consists of aluminium (Al), yttrium (Y) and gadolinium (Gd). The anatase phase of the thin films was observed and it was found that the crystal size became smaller when the concentration of thin film increased. The grain size was found to be 0.487 to 13.925 nm. The types of surface morphologies of the thin films were nanoporous, with a little agglomeration and smaller nanoparticles corresponding to Al doped TiO₂, Y doped TiO₂ and Gd doped TiO₂, respectively. The trivalent doping concentration of the thin films increased with a rising of thickness of the thin film. This can contribute to the defects that give advantages to the thin film when the mobility of the hole carriers is high and the electrons of Ti can move easily. Thus, Ti³⁺ existed as a defect state in the metal doped TiO₂ thin film based on lattice distortion with a faster growth thin film that encouraged the formation of a higher level of oxygen vacancy defects.

Ti³⁺ state in metal doped TiO₂ based on lattice distortion that encouraged the formation of oxygen vacancy defects.     

Why the thin film form of a photocatalyst is better than the particulate form for direct solar-to-hydrogen conversion: a poor man's approach

We demonstrated an easy method to improve the efficiency of photocatalysts by an order of magnitude by maximizing light absorption and charge carrier diffusion. Degussa titania (P25) and Pd/P25 composite photocatalyst thin films coated over regular glass plates were prepared and evaluated for solar hydrogen production in direct sunlight with aqueous methanol. It is worth noting that only UV light present in direct sunlight (∼4%) was absorbed by the catalysts. The hydrogen production activities of catalysts were compared for thin film and particulate forms at 1 and 25 mg levels. The hydrogen yield values suggested that 1 mg thin film form of Pd/P25 provided 11–12 times higher activity than 25 mg powder form. Comparable light absorption throughout the entire thickness of photocatalyst device and better contact of nanostructures that enabled the charge diffusion and charge utilization at redox sites are the reasons for high efficiency. While solar cells require charge carriers to diffuse through long distances of microns, they are utilized locally in an ensemble of particles (of nanometres) for hydrogen generation in photocatalyst thin films; this concept was used effectively in the present work.

Maximizing light absorption throughout the thin film and effective charge carrier utilization helped improve H₂ yield by an order of magnitude.     

Mesoporous anodic α-Fe2O3 interferometer for organic vapor sensing application

In this work, we reported the utilization of mesoporous α-Fe₂O₃ films as optical sensors for detecting organic vapors. The mesoporous α-Fe₂O₃ thin films, which exhibited obvious Fabry–Perot interference fringes in the reflectance spectrum, were successfully fabricated through electrochemical anodization of Fe foils. Through monitoring the optical thickness of the interference fringes, three typical organic species with different vapor pressures and polarities (hexane, acetone and isopropanol) were applied as probes to evaluate the sensitivity of the α-Fe₂O₃ based interferometric sensor. The experiment results showed that the as-synthesized mesoporous α-Fe₂O₃ interferometer displayed high reversibility and stability for the three organic vapors, and were especially sensitive to isopropanol, with a detection limit of about 65 ppmv. Moreover, the photocatalytic properties of α-Fe₂O₃ under visible light are beneficial for degradation of dodecane vapor residues in the nano-pores and refreshment of the sensor, demonstrating good self-cleaning properties of the α-Fe₂O₃-based interferometric sensor.

Mesoporous α-Fe₂O₃ interferometers with well-resolved optical fringes can display high sensitivity to organic vapors.     

Synthesis and characterisation of fluorinated epitaxial films of BaFeO2F: tailoring magnetic anisotropy via a lowering of tetragonal distortion

In this article, we report on the synthesis and characterisation of fluorinated epitaxial films of BaFeO₂F via low-temperature fluorination of thin films of BaFeO_2.5+d grown by pulsed laser deposition. Diffraction measurements show that fluoride incorporation only results in a contraction of the film perpendicular to the film surface, where clamping by the substrate is prohibitive for strong in-plane changes. The fluorinated films were found to be homogenous regarding the fluorine content over the whole film thickness, and can be considered as single crystal equivalents to the bulk phase BaFeO₂F. Surprisingly, fluorination resulted in the change of the tetragonal distortion to a nearly cubic symmetry, which results in a lowering of anisotropic orientation of the magnetic moments of the antiferromagnetically ordered compound, confirmed by Mössbauer spectroscopy and magnetic studies.

Fluorination of epitaxially grown thin films of BaFeO_2.5 to BaFeO₂F results in increased magnetic anisotropy.