Twofold Porosity and Surface Functionalization Effect on Pt-Porous GaN for High-Performance H2-Gas Sensors at Room Temperature.
ABSTRACT: The achievement of H2 detection, up to 25 ppm, at room temperature using sulfur-treated, platinum (Pt)-decorated porous GaN is reported in this study. This achievement is attributed to the large lateral pore size, Pt catalyst, and surface treatment using organic sulfide. The performance of H2-gas sensors is studied as a function of the operating temperature by providing an adsorption activation energy of 22 meV at 30 ppm H2, confirming the higher sensitivity of the sulfide-treated Pt-porous GaN sensor. Furthermore, the sensing response of the sulfide-treated Pt-porous GaN gas sensor increases with the increase in porosity (surface-to-volume ratio) and pore radii. Using the Knudsen diffusion-surface reaction equation, the H2 gas concentration profile is simulated and fitted within the porous GaN layer, revealing that H2 diffusion is limited by small pore radii because of its low diffusion rate. The simulated gas sensor responses to H2 versus the pore diameter show the same trend as observed for the experimental data. The sulfide-treated Pt-porous GaN sensor achieves ultrasensitive H2 detection at room temperature for 125 nm pore radii.
Project description:Photoacoustic (PA) detection of H2 and NH3 using plasmonic excitation in Pt- and Pd-decorated GaN piezotransistive microcantilevers were investigated using pulsed 520-nm laser illumination. The sensing performances of 1-nm Pt and Pd nanoparticle (NP) deposited cantilever devices were compared, of which the Pd-coated sensor devices exhibited consistently better sensing performance, with lower limit of detection and superior signal-to-noise ratio (SNR) values, compared to the Pt-coated devices. Among the two functionalization layers, Pd-coated devices were found to respond only to H2 exposure and not to NH3, while Pt-coated devices exhibited repeatable response to both H2 and NH3 exposures, highlighting the potential of the former in performing selective detection between these reducing gases. Optimization of the device-biasing conditions were found to enhance the detection sensitivity of the sensors.
Project description:Tailoring the morphology of Pt nanocrystals (NCs) is of great concern for their enhancement in catalytic activity and durability. In this article, a novel synthetic strategy is developed to selectively prepare porous dendritic Pt NCs with different structures for oxygen reduction reaction (ORR) assisted by NH3 gas and halides (F(-), Cl(-), Br(-)). The NH3 gas plays critical roles on tuning the morphology. Previously, H2 and CO gas are reported to assist the shape control of metallic nanocrystals. This is the first demonstration that NH3 gas assists the Pt anisotropic growth. The halides also play important role in the synthetic strategy to regulate the formation of Pt NCs. As-made porous dendritic Pt NCs, especially when NH4F is used as a regulating reagent, show superior catalytic activity for ORR compared with commercial Pt/C catalyst and other previously reported Pt-based NCs.
Project description:Development of in-born porous nature of zirconium hydroxide nanopowders through a facile hydrogen (H2) gas-bubbles assisted borohydride synthesis route using sodium borohydride (NaBH4) and novel information on the temperature-mediated phase transformation, pore geometry as well as pore hysteresis transformation of in-born porous zirconium hydroxide nanopowders with the help of X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) isotherm and Transmission Electron Microscopy (TEM) images are the main theme of this research work. Without any surfactants or pore forming agents, the borohydride derived amorphous nature of porous powders was stable up to 500 °C and then the seed crystals start to develop within the loose amorphous matrix and trapping the inter-particulate voids, which led to develop the porous nature of tetragonal zirconium oxide at 600 °C and further sustain this porous nature as well as tetragonal phase of zirconium oxide up to 800 °C. The novel hydrogen (H2) gas-bubbles assisted borohydride synthesis route led to develop thermally stable porous zirconium hydroxide/oxide nanopowders with an adequate pore size, pore volume, and surface area and thus these porous materials are further suggested for promising use in different areas of applications.
Project description:In view of the low sensitivity, high operating temperature and poor selectivity of acetone measurements, in this paper much effort has been paid to improve the performance of acetone sensors from three aspects: increasing the surface area of the material, improving the surface activity and enhancing gas diffusion. A hierarchical flower-like Pt-doped (1 wt %) 3D porous SnO2 (3DPS) material was synthesized by a one-step hydrothermal method. The micropores of the material were constructed by subsequent annealing. The results of the experiments show that the 3DPS-based sensor's response is strongly dependent on temperature, exhibiting a mountain-like response curve. The maximum sensor sensitivity (Ra/Rg) was found to be as high as 505.7 at a heating temperature of 153 °C and with an exposure to 100 ppm acetone. Additionally, at 153 °C, the sensor still had a response of 2.1 when exposed to 50 ppb acetone gas. The 3DPS-based sensor also has an excellent selectivity for acetone detection. The high sensitivity can be explained by the increase in the specific surface area brought about by the hierarchical flower-like structure, the enhanced surface activity of the noble metal nanoparticles, and the rapid diffusion of free-gas and adsorbed gas molecules caused by the multiple channels of the microporous structure.
Project description:Minimizing Pt loading is essential for designing cost-effective water electrolyzers and fuel cell systems. Recently, three-dimensional macroporous open-pore electroactive supports have been widely regarded as promising architectures to lower loading amounts of Pt because of its large surface area, easy electrolyte access to Pt sites, and superior gas diffusion properties to accelerate diffusion of H2 bubbles from the Pt surface. However, studies to date have mainly focused on Pt loading on Ni-based 3D open pore supports which are prone to corrosion in highly acidic and alkaline conditions. Here, we investigate electrodeposition of Pt nanoparticles in low-loading amounts on commercially available, inexpensive, 3D carbon foam (CF) support and benchmark their activity and stability for electrolytic hydrogen production. We first elucidate the effect of deposition potential on the Pt nanoparticle size, density and subsequently its coverage on 3D CF. Analysis of the Pt deposit using scanning electron microscopy images reveal that for a given deposition charge density, the particle density increases (with cubic power) and particle size decreases (linearly) with deposition overpotential. A deposition potential of -0.4 V vs. standard calomel electrode (SCE) provided the highest Pt nanoparticle coverage on 3D CF surface. Different loading amounts of Pt (0.0075-0.1 mgPt/cm2) was then deposited on CF at -0.4 V vs. SCE and subsequently studied for its hydrogen evolution reaction (HER) activity in acidic 1M H2SO4 electrolyte. The Pt/CF catalyst with loading amounts as low as 0.06 mgPt/cm2 (10-fold lower than state-of-the-art commercial electrodes) demonstrated a mass activity of 2.6 ampere per milligram Pt at 200 mV overpotential, nearly 6-fold greater than the commercial Pt/C catalyst tested under similar conditions. The 3D architectured electrode also demonstrated excellent stability, showing <7% loss in activity after 60 h of constant current water electrolysis at 100 mA/cm2.
Project description:Aqueous sodium borohydride (NaBH4) is well known for its reducing property and well-established for the development of metal nanoparticles through reduction method. In contrary, this research paper discloses the importance of aqueous NaBH4 as a precipitating agent towards development of porous zirconium oxide. The boron species present in aqueous NaBH4 play an active role during gelation as well as phase separated out in the form of boron complex during precipitation, which helps to form boron free zirconium hydroxide [Zr(OH)4] in the as-synthesized condition. Evolved in-situ hydrogen (H2) gas-bubbles also play an important role to develop as-synthesized loose zirconium hydroxide and the presence of intra-particle voids in the loose zirconium hydroxide help to develop porous zirconium oxide during calcination process. Without any surface modification, this porous zirconium oxide quickly adsorbs almost hundred percentages of toxic lead ions from water solution within 15 minutes at normal pH condition. Adsorption kinetic models suggest that the adsorption process was surface reaction controlled chemisorption. Quick adsorption was governed by surface diffusion process and the adsorption kinetic was limited by pore diffusion. Five cycles of adsorption-desorption result suggests that the porous zirconium oxide can be reused efficiently for removal of Pb (II) ions from aqueous solution.
Project description:Controlling the morphology of Pt nanostructures can provide opportunities to greatly increase their activity and stability. Porous dendritic Pt nanotubes were successfully synthesized by a facile, cost-effective aqueous solution method at room temperature in large scale. These unique structures are porous, hollow, hierarchical, and single crystalline, which not only gives them a large surface area with high catalyst utilization, but also improves mass transport and gas diffusion. These novel Pt structures exhibited significantly improved catalytic activity (4.4 fold) for oxygen reduction reaction (ORR) and greatly enhanced durability (6.1 fold) over that of the state-of-the-art commercial Pt/C catalyst. This work provides a promising approach to the design of highly efficient next-generation electrocatalysts.
Project description:Metal organic frameworks (MOFs) have been considered as one of the most exciting porous materials discovered in the last decade. Large surface areas, high pore volumes, and tailorable pore sizes make MOFs highly promising in a variety of applications, mainly in gas separations. The number of MOFs has been increasing very rapidly, and experimental identification of materials exhibiting high gas separation potential is simply impractical. High-throughput computational screening studies in which thousands of MOFs are evaluated to identify the best candidates for target gas separation is crucial in directing experimental efforts to the most useful materials. In this work, we used molecular simulations to screen the most complete and recent collection of MOFs from the Cambridge Structural Database to unlock their CH4/H2 separation performances. This is the first study in the literature, which examines the potential of all existing MOFs for adsorption-based CH4/H2 separation. MOFs (4350) were ranked based on several adsorbent evaluation metrics including selectivity, working capacity, adsorbent performance score, sorbent selection parameter, and regenerability. A large number of MOFs were identified to have extraordinarily large CH4/H2 selectivities compared to traditional adsorbents such as zeolites and activated carbons. We examined the relations between structural properties of MOFs such as pore sizes, porosities, and surface areas and their selectivities. Correlations between the heat of adsorption, adsorbility, metal type of MOFs, and selectivities were also studied. On the basis of these relations, a simple mathematical model that can predict the CH4/H2 selectivity of MOFs was suggested, which will be very useful in guiding the design and development of new MOFs with extraordinarily high CH4/H2 separation performances.
Project description:The single-layer graphene film, when incorporated with molecular-sized pores, is predicted to be the ultimate membrane. However, the major bottlenecks have been the crack-free transfer of large-area graphene on a porous support, and the incorporation of molecular-sized nanopores. Herein, we report a nanoporous-carbon-assisted transfer technique, yielding a relatively large area (1?mm2), crack-free, suspended graphene film. Gas-sieving (H2/CH4 selectivity up to 25) is observed from the intrinsic defects generated during the chemical-vapor deposition of graphene. Despite the ultralow porosity of 0.025%, an attractive H2 permeance (up to 4.1?×?10-7?mol?m-2?s-1?Pa-1) is observed. Finally, we report ozone functionalization-based etching and pore-modification chemistry to etch hydrogen-selective pores, and to shrink the pore-size, improving H2 permeance (up to 300%) and H2/CH4 selectivity (up to 150%). Overall, the scalable transfer, etching, and functionalization methods developed herein are expected to bring nanoporous graphene membranes a step closer to reality.
Project description:Possessing a large surface-to-volume ratio is significant to the sensitive gas detection of semiconductor nanostructures. Here, we propose a fast-response ammonia gas sensor based on porous nanostructured zinc oxide (ZnO) film, which is fabricated through physical vapor deposition and subsequent thermal annealing. In general, an extremely thin silver (Ag) layer (1, 3, 5 nm) and a 100 nm ZnO film are sequentially deposited on the SiO2/Si substrate by a magnetron sputtering method. The porous nanostructure of ZnO film is formed after thermal annealing contributed by the diffusion of Ag among ZnO crystal grains and the expansion of the ZnO film. Different thicknesses of the Ag layer help the formation of different sizes and quantities of hollows uniformly distributed in the ZnO film, which is demonstrated to hold superior gas sensing abilities than the compact ZnO film. The responses of the different porous ZnO films were also investigated in the ammonia concentration range of 10 to 300 ppm. Experimental results demonstrate that the ZnO/Ag(3 nm) sensor possesses a good electrical resistance variation of 85.74% after exposing the sample to 300 ppm ammonia gas for 310 s. Interestingly, a fast response of 61.18% in 60 s for 300 ppm ammonia gas has been achieved from the ZnO/Ag(5 nm) sensor, which costs only 6 s for the response increase to 10%. Therefore, this controllable, porous, nanostructured ZnO film maintaining a sensitive gas response, fabricated by the physical deposition approach, will be of great interest to the gas-sensing community.