Shaopeng Qiao

Sub-6 nm Palladium Nanoparticles for Faster, More Sensitive H2 Detection Using Carbon Nanotube Ropes

Palladium (Pd) nanoparticle (NP)-decorated carbon nanotube (CNT) ropes (or CNT@PdNP) are used as the sensing element for hydrogen gas (H2) chemiresistors. In spite of the fact that Pd NPs have a mean diameter below 6 nm and are highly dispersed on the CNT surfaces, CNT@PdNP ropes produce a relative resistance change 20-30 times larger than is observed at single, pure Pd nanowires. Thus, CNT@PdNP rope sensors improve upon all H2 sensing metrics (speed, dynamic range, and limit-of-detection), relative to single Pd nanowires which heretofore have defined the state-of-the-art in H2 sensing performance. Specifically, response and recovery times in air at [H2] ≈ 50 ppm are one-sixth of those produced by single Pd nanowires with cross-sectional dimensions of 40 × 100 nm Pd. The LODH2 is <10 ppm versus 300 ppm, and the dynamic range (10 ppm -4%) is nearly twice that afforded by the Pd nanowire. CNT@PdNP rope sensors are prepared by the dielectrophoretic deposition of a single semiconducting CNT rope followed by the electrodeposition of Pd nanoparticles with mean diameters ranging from 4.5 (±1) nm to 5.8 (±3) nm. The diminutive mean diameter and the high degree of diameter monodispersity for the deposited Pd nanoparticles are distinguishing features of the CNT@PdNP rope sensors described here, relative to prior work on similar systems.

Accelerating Palladium Nanowire H2 Sensors Using Engineered Nanofiltration

The oxygen, O2, in air interferes with the detection of H2 by palladium (Pd)-based H2 sensors, including Pd nanowires (NWs), depressing the sensitivity and retarding the response/recovery speed in air-relative to N2 or Ar. Here, we describe the preparation of H2 sensors in which a nanofiltration layer consisting of a Zn metal-organic framework (MOF) is assembled onto Pd NWs. Polyhedron particles of Zn-based zeolite imidazole framework (ZIF-8) were synthesized on lithographically patterned Pd NWs, leading to the creation of ZIF-8/Pd NW bilayered H2 sensors. The ZIF-8 filter has many micropores (0.34 nm for gas diffusion) which allows for the predominant penetration of hydrogen molecules with a kinetic diameter of 0.289 nm, whereas relatively larger gas molecules including oxygen (0.345 nm) and nitrogen (0.364 nm) in air are effectively screened, resulting in superior hydrogen sensing properties. Very importantly, the Pd NWs filtered by ZIF-8 membrane (Pd NWs@ZIF-8) reduced the H2 response amplitude slightly (ΔR/R0 = 3.5% to 1% of H2 versus 5.9% for Pd NWs) and showed 20-fold faster recovery (7 s to 1% of H2) and response (10 s to 1% of H2) speed compared to that of pristine Pd NWs (164 s for response and 229 s for recovery to 1% of H2). These outstanding results, which are mainly attributed to the molecular sieving and acceleration effect of ZIF-8 covered on Pd NWs, rank highest in H2 sensing speed among room-temperature Pd-based H2 sensors.

Electrodeposited, Transverse Nanowire Electroluminescent Junctions

The preparation by electrodeposition of transverse nanowire electroluminescent junctions (tn-ELJs) is described, and the electroluminescence (EL) properties of these devices are characterized. The lithographically patterned nanowire electrodeposition process is first used to prepare long (millimeters), linear, nanocrystalline CdSe nanowires on glass. The thickness of these nanowires along the emission axis is 60 nm, and the width, wCdSe, along the electrical axis is adjustable from 100 to 450 nm. Ten pairs of nickel-gold electrical contacts are then positioned along the axis of this nanowire using lithographically directed electrodeposition. The resulting linear array of nickel-CdSe-gold junctions produces EL with an external quantum efficiency, EQE, and threshold voltage, Vth, that depend sensitively on wCdSe. EQE increases with increasing electric field and also with increasing wCdSe, and Vth also increases with wCdSe and, therefore, the electrical resistance of the tn-ELJs. Vth down to 1.8(±0.2) V (for wCdSe ≈ 100 nm) and EQE of 5.5(±0.5) × 10(-5) (for wCdSe ≈ 450 nm) are obtained. tn-ELJs produce a broad EL emission envelope, spanning the wavelength range from 600 to 960 nm.

Hollow Pd–Ag Composite Nanowires for Fast Responding and Transparent Hydrogen Sensors

Pd based alloy materials with hollow nanostructures are ideal hydrogen (H2) sensor building blocks because of their double-H2 sensing active sites (interior and exterior side of hollow Pd alloy) and fast response. In this work, for the first time, we report a simple fabrication process for preparing hollow Pd-Ag alloy nanowires (Pd@Ag HNWs) by using the electrodeposition of lithographically patterned silver nanowires (NWs), followed by galvanic replacement reaction (GRR) to form palladium. By controlling the GRR time of aligned Ag NWs within an aqueous Pd2+-containing solution, the compositional transition and morphological evolution from Ag NWs to Pd@Ag HNWs simultaneously occurred, and the relative atomic ratio between Pd and Ag was controlled. Interestingly, a GRR duration of 17 h transformed Ag NWs into Pd@Ag HNWs that showed enhanced H2 response and faster sensing response time, reduced 2.5-fold, as compared with Ag NWs subjected to a shorter GRR period of 10 h. Furthermore, Pd@Ag HNWs patterned on the colorless and flexible polyimide (cPI) substrate showed highly reversible H2 sensing characteristics. To further demonstrate the potential use of Pd@Ag HNWs as sensing layers for all-transparent, wearable H2 sensing devices, we patterned the Au NWs perpendicular to Pd@Ag HNWs to form a heterogeneous grid-type metallic NW electrode which showed reversible H2 sensing properties in both bent and flat states.

Pt-Functionalized PdO Nanowires for Room Temperature Hydrogen Gas Sensors

In this work, we prepared a well-aligned palladium oxide nanowire (PdO NW) array using the lithographically patterned Pd nanowire electrodeposition (LPNE) method followed by subsequent calcination at 500 °C. Sensitization with platinum (Pt) nanoparticles (NPs), which were functionalized on PdO NWs through a simple reduction process, significantly enhanced the detection capability of the Pt-loaded PdO NWs (Pt-PdO NWs) sensors toward hydrogen gas (H2) at room temperature. The well-distributed Pt NPs, which are known chemical sensitizers, activated the dissociation of H2 and oxygen molecules through the spillover effect with subsequent diffusion of these products to the PdO surface, thereby transforming the entire surface of the PdO NWs into reaction sites for H2. As a result, at a high concentration of H2 (0.2%), the Pt-PdO NWs showed an enhanced sensitivity of 62% (defined as Δ R/ Rair × 100%) compared to that (6.1%) of pristine PdO NWs. The Pt-PdO NWs exhibited a response time of 166 s, which was 2.68-fold faster than that of pristine PdO NWs (445 s). In addition, the Pt-PdO NWs responded to a very low concentration of H2 (10 ppm) with a sensitivity of 14%, unlike the pristine PdO NWs, which did not exhibit any response at that concentration. These outstanding results are mainly attributed to a homogeneous decoration of Pt NPs on the surface of well-aligned PdO NWs. In this work, we demonstrated the potential suitability of Pt-PdO NWs as a highly sensitive H2 sensing layer at room temperature.

Hierarchical Metal–Organic Framework-Assembled Membrane Filter for Efficient Removal of Particulate Matter

Here, we propose heterogeneous nucleation-assisted hierarchical growth of metal-organic frameworks (MOFs) for efficient particulate matter (PM) removal. The assembly of two-dimensional (2D) Zn-based zeolite imidazole frameworks (2D-ZIF-L) in deionized water over a period of time produced hierarchical ZIF-L (H-ZIF-L) on hydrophilic substrates. During the assembly, the second nucleation and growth of ZIF-L occurred on the surface of the first ZIF-L, leading to the formation of flowerlike H-ZIF-L on the substrate. The flowerlike H-ZIF-L was easily synthesized on various substrates, namely, glass, polyurethane three-dimensional foam, nylon microfibers, and nonwoven fabrics. We demonstrated H-ZIF-L-assembled polypropylene microfibers as a washable membrane filter with highly efficient PM removal property (92.5 ± 0.8% for PM2.5 and 99.5 ± 0.2% for PM10), low pressure drop (10.5 Pa at 25 L min-1), long-term stability, and superior recyclability. These outstanding particle filtering properties are mainly attributed to the unique structure of the 2D-shaped H-ZIF-L, which is tightly anchored on individual fibers comprising the membrane.