Вы находитесь на странице: 1из 2


E.C. Walter, F. Favier, E.J. Menke, R.M. Penner*

Department of Chemistry University of California, Irvine Irvine, CA 92697-2025

Introduction Hydrogen has tremendous potential as an environmentally friendly fuel for vehicles, cell phones, laptop computers, and other mobile devices. But hydrogen-air mixtures are explosive for [H 2 ] > 4%, and hydrogen leak detection is therefore of considerable importance. Ideally, sensors for leaked hydrogen will be small, power-efficient, inexpensive, and fast in terms of the rate of sensor response. In this presentation, we describe a new type of H 2 sensor based on an emerging nanotechnology. This sensor consists of a parallel array of 10 to 100 of palladium nanowires, as shown in Figure 1 1,2 . The resistance of this palladium nanowire array (PNA) was measured by applying a voltage of a few millivolts, and monitoring the current that is of the order of microamps.

monitoring the current that is of the order of microamps. Figure 1. Schematic diagram of a

Figure 1. Schematic diagram of a hydrogen sensor based on a palladium nanowire array (PNA).

Although PNAs are an immature technology for H 2 sensing (the first PNA-based H 2 sensor was prepared in April 2001), early versions of these devices exhibit many desirable properties for H 2 leak detection. The preparation of H 2 sensors based on electrodeposited palladium nanowire arrays (PNAs) and the performance of these sensors for detecting hydrogen are both discussed.

Experimental Electrochemical measurements. All chemicals were reagent grade from Fisher and were used without further purification. Two different Pd plating solutions were used: aqueous 2 mM PdCl 2 , 0.1 M HCl and 2 mM Pd(NO 3 ) 2 , 0.1 M HClO 4 . Barnstead Nanopure deionized water (_ > 17.8 M_) was employed for all solutions. Pd plating solutions were purged for 10 minutes with pre-humidified N 2 prior to use. Cyclic voltammograms (CVs) and potentiostatic metal plating pulses were applied using an EG&G model 263A potentiostat. All deposition experiments were carried out in a glass electrochemical cell. Highly oriented pyrolytic graphite was freshly cleaved with adhesive tape and held using a Teflon electrode holder. Approximately 0.3 cm 2 of this graphite sample was exposed to the Pd plating solution in the electrochemical cell. A saturated calomel reference electrode (SCE) was employed as the reference electrode.


platinum foil (4 cm 2 ) was employed as the counter electrode in



Sensor Fabrication. Briefly, the surface of the graphite electrode onto which Pd nanowires had been deposited was pressed onto a droplet (50 µl) of cyanoacrylate adhesive ("Special T" super glue, Satellite City) on a degreased glass slide. After this adhesive hardened, the graphite surface was lifted off the cyanoacrylate, and residual carbon layers were removed with a forceps. The vast majority the nanowires initially present on the graphite surface were transferred onto the surface of the cyanoacrylate film using this procedure. Silver contacts (conductive liquid silver, Ted Pella) were manually applied to the two ends of a nanowire array using a thin glass pipette and copper wires were attached to these contacts to facilitate resistance measurements. Hydrogen Sensing. Most sensor measurements were carried out in a sealed 50 mL glass jar to which gas inlets and outlets had been attached. A MKS type 647B mass flow and pressure programmer was used in conjunction with an MKS mass flow controller to produce a flow rate of 200 sccm (+ 2 sccm) in all gas flow measurements. The response time of this controller was <100 ms. Sensor response times were measured in a % smaller volume cell having a dead volume of 1 mL, using gas flow rates of 200 sccm through a solenoid valve with a switching time of 10 ms. Sensor currents were measured using a potentiostat (EG&G model 263A) which also provided a bias of 5 or 10 mV.

model 263A) which also provided a bias of 5 or 10 mV. Figure 2. (a) Palladium

Figure 2. (a) Palladium nanowires prepared by electrodeposition on graphite. (b) A PNA after transfer to a cyanoacrylate film and the application of silver contacts.

Results and Discussion Palladium nanowires and a PNA are shown in the scanning electron micrographs shown in Figure 2. These nanowires were prepared by electrodepositing palladium metal from a dilute, aqueous plating solution, onto a highly oriented pyrolytic graphite electrode surface. Nanowire growth is obtained by applying three voltage pulses in rapid succession: A +1.2V x 5s “conditioning” pulse, a – 0.20 V x 10 ms “nucleation” pulse, and a +0.30 V x 10 min. “growth” pulse (all voltages vs. SCE). These deposition conditions

Fuel Chemistry Division Preprints 2002 , 47(2), 828

produced polycrystalline palladium nanowires with diameters in 200-300 nm range (Fig. 2a). These nanowires, which were 100 µm to 500 µm in length, nucleated and grew at step edges on the graphite surface. Growth at step edges occurs because the energetic barrier to palladium nucleation is somewhat lower at these defect structures as compared with atomically smooth and defect-free terraces. Following the electrodeposition of palladium nanowires, many (i.e., 20 or more) arrays of nanowires are present on the graphite electrode surface. These arrays consist of between 20 and 200 Pd nanowires arranged in parallel. The response of a PNA sensor to mixtures of H 2 and N 2 are shown in Figure 3a. Most sensors exhibited a large resistance (> 1.0 M) in the absence of H 2 (below 0.5%). At a threshold of 2% H 2 , these “mode II” sensors became conductive and the resistance of the PNA decreased by a factor of 1/10 as the H 2 concentration increased from 2% to 10% (Fig. 3b). Some sensors exhibited an appreciable resistance even in the absence of H 2 (data not shown). These “mode I” sensors also exhibited a lower threshold for detecting H 2 of approx. 0.5 % (Fig. 3b). 1,2

for detecting H 2 of approx. 0.5 % (Fig. 3b). 1 , 2 Figure 3. (a)

Figure 3. (a) Response of a mode II PNA sensor to hydrogen/N 2 mixtures as a function of concentration. (b) Calibration plots for typical mode I and mode II PNA sensors.

The response of PNA-based sensors was exactly the opposite expected based on the materials properties of the palladium/hydrogen system. 3 Alloys of palladium hydrides have a higher electrical conductivity than pure palladium and H 2 sensors based on palladium resistors respond to hydrogen exposure by becoming more resistive. The unexpected increased conductance of PNA-based H 2 sensors was caused by the presence of nanoscopic breaks in the nanowires in the PNA. 1,2 These breaks are visible in SEM images, such as the one shown in Figure 4. These nanoscopic breaks function as “break junctions” that close in the presence of H2, and open in its absence, as shown in Figure 5. This surprising behavior is caused by the swelling of the palladium-hydride lattice by 3% as the hydrogen content of the metal increases from pure Pd to PdH 0.7 . 3

of the metal increases from pure Pd to PdH 0 . 7 . 3 Figure 4.

Figure 4. Scanning electron microscopy image of break junctions in the palladium nanowires of a functioning PNA-based H 2 sensor. These break junctions form the basis for sensor function.

These break junctions form the basis for sensor function. Figure 5. Schematic depiction of the formation

Figure 5. Schematic depiction of the formation of break junctions, and the operation of a break junction in a palladium nanowire.

Summary Arrays of palladium nanowires, prepared by electrodeposition, can be used to detect H2. Individual palladium nanowires in these arrays fracture upon exposure to hydrogen gas, and the resulting nanoscopic gaps function as hydrogen-actuated “break junctions”. Exposure of PNAs to hydrogen causes break junctions in the nanowires to close causing individual nanowires in the array to switch from an insulating to a conducting state. This response to hydrogen is rapid (as fast as 20 ms) and selective. Acknowledgment. This work was funded by the NSF (grant CHE-0111557) and the UC BioStar Program in conjunction with Nanomix Inc. (Emeryville, CA). F.F. acknowledges funding through NATO. Donations of graphite by Dr. Art Moore of Advanced Ceramics Inc. are gratefully acknowledged.


1. Favier, F., Walter, E.C., Penner, R.M., Science 2001, 293, 2227-31.

2. Walter, E.C., Favier, F., Penner, R.M., Anal. Chem. 2002, 74, 1546-52.

3. Lewis, F. A. The Palladium Hydrogen System; Academic Press: New York, 1967.

Fuel Chemistry Division Preprints 2002 , 47(2), 879